Compound, (co)polymer, composition, method for forming a resist pattern, and method for manufacturing the compound and (co)polymer

Abstract

Iodine-containing (meth)acrylate compound represented by formula (1). In formula (1), R1 represents a hydrogen atom, a methyl group, or a halogen, and R2 each independently represents a hydrogen atom, a straight-chain organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms, A represents an organic group having 1 to 30 carbon atoms, A includes at least one acyl group, n1 represents 0 or 1, and n2 represents an integer from 1 to 20.

Description

Technology Field

[0001] The present invention relates to a compound, a (co)polymer, a composition, a method for forming a resist pattern, and a method for manufacturing a compound and a (co)polymer. Background Technology

[0002] Recently, in the manufacturing of semiconductor devices and liquid crystal display devices, the miniaturization of semiconductors (patterns) and pixels is progressing rapidly due to advancements in lithography technology. Generally, the short wavelength of the exposure light source is used as a method for pixel miniaturization. Specifically, while ultraviolet rays represented by g-rays and i-rays were conventionally used, far-ultraviolet lithography, such as KrF excimer lasers (248 nm) and ArF excimer lasers (193 nm), is currently becoming the center of mass production, and furthermore, the introduction of Extreme Ultraviolet (EUV) lithography (13.5 nm) is underway. In addition, electron beams (EB) are also being utilized for the formation of fine patterns.

[0003] General resist materials include polymeric resist materials capable of forming an amorphous film, such as polymethyl methacrylate, polyhydroxystyrene having acid-dissociating groups, or polyalkyl methacrylate (see, for example, Non-Patent Literature 1).

[0004] Conventionally, a line pattern of about 10 to 100 nm is formed by irradiating a resist thin film, which is fabricated by applying a solution of these resist materials onto a substrate, with ultraviolet rays, far ultraviolet rays, electron beams, extreme ultraviolet rays, X-rays, etc.

[0005] Furthermore, the reaction mechanism of electron beam or extreme ultraviolet lithography differs from that of conventional photolithography. Moreover, electron beam or extreme ultraviolet lithography aims to form fine patterns ranging from several nanometers to tens of nanometers. As the resist pattern size decreases in this way, resist materials with even higher sensitivity to the exposure light source are required. Particularly in extreme ultraviolet lithography, further sensitivity enhancement is required in terms of throughput.

[0006] As a resist material that improves the problem described above, inorganic resist materials having metal elements such as titanium, tin, hafnium, and zirconium have been proposed (see, for example, Patent Document 1). Prior art literature

[0007] Japanese Patent Publication No. 2015-108781

[0008] Shinji Okazaki et al., *40 Years of Lithography Technology*, S&T Publishing, published December 9, 2016 The problem to be solved

[0009] However, since the compounds and (co)polymers used in conventional resist materials have low stability, there are problems such as poor stability and productivity of the compounds and (co)polymers.

[0010] In addition, conventionally developed resist materials have many film defects and problems such as insufficient sensitivity, insufficient etching resistance, or defective resist patterns. In particular, it is difficult to achieve both high resolution and high sensitivity because there is a trade-off relationship between resolution and sensitivity.

[0011] Furthermore, (co)polymers having hydroxyl groups are useful as resist materials, but there is a problem that the productivity of these (co)polymers is poor because the stability of the raw material compounds and (co)polymers is low.

[0012] Taking the above circumstances into account, the present invention aims to provide a compound and a method for manufacturing the compound, a (co)polymer and a composition, which are capable of forming a film that is compatible with resist materials, has high stability, high sensitivity, and high resolution, and a method for forming a resist pattern using the composition. In addition, the invention aims to provide a method for manufacturing a (co)polymer having hydroxyl groups that are useful for resist materials and have high productivity. means of solving the problem

[0013] As a result of careful consideration to solve the problem described above, the inventors discovered that a compound and a (co)polymer having a specific structure, and a composition comprising these compounds and (co)polymers, can form a film having high stability, high sensitivity, and high resolution, and are suitable for resist materials, thereby completing the present invention.

[0014] In addition, since the stability of the compound and (co)polymer having a specific structure is high, it was discovered that by using this (co)polymer, a (co)polymer having hydroxyl groups useful for resist materials can be efficiently manufactured, leading to the completion of the present invention.

[0015] That is, the present invention is as follows.

[0016] [1]

[0017] Iodine-containing (meth)acrylate compound represented by formula (1).

[0018] [Chemical Formula 1]

[0019]

[0020] (In the formula (1),

[0021] R 1 Representing silver, hydrogen atoms, methyl groups, or halogens,

[0022] R 2Each independently represents a hydrogen atom, a straight-chain organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms, and

[0023] A represents an organic group having 1 to 30 carbon atoms, and

[0024] A comprises at least one acyl group, and

[0025] n 1 represents 0 or 1, and

[0026] n 2 represents an integer from 1 to 20.

[0027] [1-1]

[0028] n 1 The iodine-containing (meth)acrylate compound described in [1], which is a carbon aliquot having 5 to 30 carbon atoms, where A may have a substituent.

[0029] [1-2]

[0030] An iodine-containing (meth)acrylate compound described in [1-1], wherein the carbon aliquot having 5 to 30 carbon atoms that may have the above substituent is an adamantane that may have the substituent.

[0031] [2]

[0032] The above formula (1) is the iodine-containing (meth)acrylate compound described in [1], which is formula (2).

[0033] [Chemical Formula 2]

[0034]

[0035] (In Equation (2), R 1 , A, and n 2 is the same as above.).

[0036] [3]

[0037] The above formula (2) is the iodine-containing (meth)acrylate compound described in [2], which is formula (3).

[0038] [Chemical Formula 3]

[0039]

[0040] (Eating(3) in,

[0041] B represents an organic group having 5 to 30 carbon atoms including an aromatic group, B comprises at least one acyl group, and R 1 , and n 2 is the same as above.).

[0042] [3-1]

[0043] B is an iodine-containing (meth)acrylate compound described in [3], which may have a substituent and is an aromatic compound having 5 to 30 carbon atoms.

[0044] [3-2]

[0045] An iodine-containing (meth)acrylate compound described in [3-1], wherein the aromatic group having 5 to 30 carbon atoms that may have the above substituent is a benzene that may have the substituent.

[0046] [4]

[0047] The above formula (2) is the iodine-containing (meth)acrylate compound described in [2], which is formula (3').

[0048] [Chemical Formula 4]

[0049]

[0050] (In formula (3'), B' represents an organic group having 5 to 30 carbon atoms including a ring, B' includes at least one acyl group, and R 1 , and n 2 is the same as above.).

[0051] [4-1]

[0052] B' is an iodine-containing (meth)acrylate compound described in [4], which is a carbon aliquot having 5 to 30 carbon atoms and may have a substituent.

[0053] [4-2]

[0054] The iodine-containing (meth)acrylate compound described in [4-1], wherein the carbon aliquot having 5 to 30 carbon atoms that may have the above substituent is an adamantane that may have the substituent.

[0055] [5]

[0056] n 2 An iodine-containing (meth)acrylate compound described in any one of [1] to [4-2], wherein is an integer from 2 to 20.

[0057] [6]

[0058] Iodine-containing (meth)acrylate (co)polymer having a constituent unit represented by formula (4).

[0059] [Chemical Formula 5]

[0060]

[0061] (Essence (4),

[0062] R 1 Representing silver, hydrogen atoms, methyl groups, or halogens,

[0063] R 2 Each independently represents a hydrogen atom, a straight-chain organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms, and

[0064] A represents an organic group having 1 to 30 carbon atoms, and

[0065] A comprises at least one acyl group, and

[0066] n 1 represents 0 or 1, and

[0067] n 2 represents an integer from 1 to 20, and

[0068] The symbol * indicates the connection point with an adjacent constituent unit.

[0069] [6-1]

[0070] n 1The iodine-containing (meth)acrylate (co)polymer described in [6], which is a carbon aliquot having 5 to 30 carbon atoms, in which A may have a substituent.

[0071] [6-2]

[0072] The iodine-containing (meth)acrylate (co)polymer described in [6-1], wherein the carbon aliquot having 5 to 30 carbon atoms that may have the above substituents is an adamantane that may have the substituents.

[0073] [7]

[0074] The above formula (4) is the iodine-containing (meth)acrylate (co)polymer described in [6], which is formula (5).

[0075] [Chemical Formula 6]

[0076]

[0077] (In Equation (5), R 1 , n 2 , A, and the symbol* are the same as above.).

[0078] [8]

[0079] The above formula (5) is the iodine-containing (meth)acrylate (co)polymer described in [7], which is formula (6).

[0080] [Chemical Formula 7]

[0081]

[0082] (In formula (6), B represents an organic group having 5 to 30 carbon atoms including an aromatic group, B includes at least one acyl group, and R 1 , n 2 , and the symbol* are the same as above.).

[0083] [8-1]

[0084] B is an iodine-containing (meth)acrylate (co)polymer described in [8], which may have a substituent and is an aromatic carbon atom having 5 to 30 carbon atoms.

[0085] [8-2]

[0086] The iodine-containing (meth)acrylate (co)polymer described in [8-1], wherein an aromatic group having 5 to 30 carbon atoms that may have the above substituents is a benzene that may have the substituents.

[0087] [9]

[0088] The above formula (5) is the iodine-containing (meth)acrylate (co)polymer described in [7], which is formula (6').

[0089] [Chemical Formula 8]

[0090]

[0091] (In formula (6'), B' represents an organic group having 5 to 30 carbon atoms including a ring, B' includes at least one acyl group, and R 1 , n 2 , and the symbol* are the same as above.).

[0092] [9-1]

[0093] B' is an iodine-containing (meth)acrylate (co)polymer described in [9], which is a carbon aliquot having 5 to 30 carbon atoms that may have a substituent.

[0094] [9-2]

[0095] The iodine-containing (meth)acrylate (co)polymer described in [9-1], wherein the carbon aliquot having 5 to 30 carbon atoms that may have the above substituents is an adamantane that may have the substituents.

[0096]

[10]

[0097] n 2 Iodine-containing (meth)acrylate (co)polymer described in any one of [6] to [9-2], where is an integer from 2 to 20.

[0098]

[11]

[0099] A composition comprising an iodine-containing (meth)acrylate compound described in any one of [1] to [5], and / or an iodine-containing (meth)acrylate (co)polymer described in any one of [6] to

[10] .

[0100]

[12]

[0101] A composition described in

[11] that additionally contains a solvent.

[0102]

[13]

[0103] A composition described in

[11] or

[12] that additionally contains an acid-generating agent.

[0104]

[14]

[0105] A composition described in any one of

[11] to

[13] that additionally contains an acid diffusion control agent.

[0106]

[15]

[0107] A process for forming a film using a composition described in any one of

[11] ~

[14] , and

[0108] A process for exposing the film formed in the above process, and

[0109] A method for forming a resist pattern, comprising a process of removing an exposed portion of a film exposed in the above process using a developer to form a pattern.

[0110]

[16]

[0111] A process of reacting an iodine-containing hydroxyl compound represented by formula (a) with a (meth)acrylic acid compound represented by formula (b), and

[0112] A method for producing an iodine-containing (meth)acrylate compound as described in any one of [1] to [5], comprising a process of reacting an acylating agent with a reactant obtained from the above process.

[0113] [Chemical Formula 9]

[0114]

[0115] (in formula (a), A' represents an organic group having 1 to 30 carbon atoms, A' has at least one hydroxyl group, and R 2 , n 1 , and n 2 is the same as above.)

[0116] [Chemical Formula 10]

[0117]

[0118] (in Equation (b), R 1 Eun is identical to the above, and R B Is , It is a hydroxyl group, halogen, (meth)acryloyloxy group, or alkoxy group.)

[0119] [16-1]

[0120] In equation (a), n 1 A method for preparing an iodine-containing (meth)acrylate compound as described in

[16] , wherein the aliquot has 5 to 30 carbon atoms and A' may have a substituent, and A' has at least one hydroxyl group.

[0121] [16-2]

[0122] A method for preparing an iodine-containing (meth)acrylate compound as described in [16-1], wherein a carbon aliquot having 5 to 30 carbon atoms that may have the above substituent is an adamantane that may have the substituent.

[0123]

[17]

[0124] A method for preparing an iodine-containing (meth)acrylate compound as described in

[16] , wherein the above formula (a) is formula (a1).

[0125] [Chemical Formula 11]

[0126]

[0127] (in Equation (a1), A', and n 2 is the same as above.).

[0128]

[18]

[0129] A method for preparing an iodine-containing (meth)acrylate compound as described in

[16] , wherein the above formula (a) is formula (a2).

[0130] [Chemical Formula 12]

[0131]

[0132] (In formula (a2), B'' represents an organic group having 5 to 30 carbon atoms including an aromatic group, B'' has at least one hydroxyl group, and n 2 is the same as above.).

[0133] [18-1]

[0134] A method for preparing an iodine-containing (meth)acrylate compound as described in

[18] , wherein B'' in formula (a2) is an aromatic compound having 5 to 30 carbon atoms that may have a substituent, and B'' has at least one hydroxyl group.

[0135] [18-2]

[0136] A method for preparing an iodine-containing (meth)acrylate compound as described in [18-1], wherein an aromatic group having 5 to 30 carbon atoms that may have the above substituent is a benzene that may have the substituent.

[0137]

[19]

[0138] A method for preparing an iodine-containing (meth)acrylate compound as described in

[16] , wherein the above formula (a) is formula (a3).

[0139] [Chemical Formula 13]

[0140]

[0141] (in formula (a3), B''' represents an organic group having 5 to 30 carbon atoms including a cycloaliphatic group, B''' has at least one hydroxyl group, and n 2 is the same as above.).

[0142] [19-1]

[0143] A method for preparing an iodine-containing (meth)acrylate compound as described in

[19] , wherein B''' in formula (a3) ​​is a carbon aliquot having 5 to 30 carbon atoms that may have a substituent, and B''' has at least one hydroxyl group.

[0144] [19-2]

[0145] A method for preparing an iodine-containing (meth)acrylate compound as described in [19-1], wherein a carbon aliquot having 5 to 30 carbon atoms that may have the above substituent is an adamantane that may have the substituent.

[0146]

[20]

[0147] n 2 A method for preparing an iodine-containing (meth)acrylate compound as described in any one of

[16] to

[19] , wherein the value is an integer from 2 to 20.

[0148]

[21]

[0149] A method for producing a (co)polymer having a hydroxyl group represented by formula (Y), comprising a process of hydrolyzing an acyl group in an iodine-containing (meth)acrylate (co)polymer described in any one of [6]~[9].

[0150] [Chemical Formula 14]

[0151]

[0152] (among Equation(Y),

[0153] R 1 Representing silver, hydrogen atoms, methyl groups, or halogens,

[0154] R 2 Each independently represents a hydrogen atom, a straight-chain organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms, and

[0155] A' represents an organic group having 1 to 30 carbon atoms, and

[0156] A' has at least one hydroxyl group,

[0157] n 1 represents 0 or 1, and

[0158] n 2 represents an integer from 1 to 20, and

[0159] The symbol * indicates the connection point with an adjacent constituent unit. Effects of the invention

[0160] According to the present invention, a compound and a method for preparing the compound, a (co)polymer and a composition, and a method for forming a resist pattern using the composition can be provided, which is capable of forming a film that is compatible with resist materials, has high stability, high sensitivity, and high resolution. In addition, by using the compound and the (co)polymer, a method can be provided to efficiently produce a (co)polymer having hydroxyl groups useful for resist materials. Specific details for implementing the invention

[0161] Hereinafter, embodiments of the present invention will be described (hereinafter referred to as “the present embodiment”). Meanwhile, the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.

[0162] In this specification, (meth)acrylate means acrylate and methacrylate. Other terms having the expression (meth)acrylate are interpreted in the same way as (meth)acrylate.

[0163] In this specification, (co)polymer means homopolymer and copolymer.

[0164] [Iodine-containing (meth)acrylate compounds]

[0165] The iodine-containing (meth)acrylate compound of the present embodiment (simply referred to as the “compound”) is represented by the following formula (1). Since the compound has high stability, it can be produced efficiently. In addition, the compound can achieve high sensitivity in the lithography process and can form a film with high resolution. Furthermore, the (co)polymer containing the compound as a constituent unit also has high stability, and the iodine-containing (meth)acrylate (co)polymer (simply referred to as the “(co)polymer”) can be produced efficiently.

[0166] [Chemical Formula 15]

[0167]

[0168] In Equation (1), R 1 Representing silver, a hydrogen atom, a methyl group, or a halogen, R 2 Each represents, independently, a hydrogen atom, a straight-chain organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms, A represents an organic group having 1 to 30 carbon atoms, A comprises at least one acyl group, and n 1 represents 0 or 1, and n 2 represents an integer from 1 to 20.

[0169] R 1 Silver, hydrogen atoms, methyl groups, or halogens may be used. As halogens, known atoms may be used, and fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), etc., may be suitablely used. R 1 In terms of exposure sensitivity and material stability when the compound of the present embodiment is used as a constituent unit of a resin for a resist, it is preferable that it be a methyl group or a halogen, and it is more preferable that it be a methyl group in terms of superior stability. In addition, considering the superior exposure sensitivity, R 1 It is more preferable that it be a halogen, and even more preferable that it be iodine (I).

[0170] R 2 It may be a combination of two or more selected from the group consisting of a straight-chain organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, and a cyclic organic group having 3 to 20 carbon atoms.

[0171] R 2It is preferable that the element be a hydrogen atom for the purpose of enhancing the effect of introducing iodine by suppressing the rise in the Tg (glass transition temperature) of the resin. Meanwhile, it is also preferable that the element be an organic group having one or more carbon atoms for the purpose of controlling solubility in the developer and improving acid decomposition. Furthermore, it is more preferable that the element be a hydrogen atom for the purpose of suppressing acid decomposition, particularly ensuring solubility in an alkaline developer, and suppressing residue.

[0172] R 2 may have substituents. R 2 The group comprises, for example, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, which may have a substituent; an alkenyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, which may have a substituent; an alkynyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, which may have a substituent; a cycloalkyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, which may have a substituent; a cycloalkenyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, which may have a substituent; and a cycloalkynyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, which may have a substituent. Examples include an aryl group having 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms, more preferably 5 to 6 carbon atoms, which may have a substituent; combinations thereof.

[0173] R 2Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, icosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloicosyl, adamantyl, ethylene, propylene, butylene, phenyl, naphthyl, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, benzopyrene, azulene, and fluorene groups, which may have substituents. These groups may include ether bonds, ketone bonds, and ester bonds.

[0174] In the present embodiment, the group being exemplified includes isomers. Examples of such isomers include, if it is a propyl group, n-propyl group and isopropyl group, and if it is a butyl group, n-butyl group, sec-butyl group, isobutyl group, and tert-butyl group.

[0175] R 2 The substituents are not particularly limited, but examples include halogens, hydroxyl groups, cyano groups, nitro groups, amino groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aracleyl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkylloyloxy groups, aryloyloxy groups, and alkylsilyl groups, as well as various crosslinking groups and acid dissociating groups.

[0176] "Crossifying group" refers to a group that crosslinks by acid, alkali, light, or heat, and crosslinks in the presence or absence of a catalyst. The above-mentioned crosslinking group is not particularly limited, but examples include a group having an allyl group, a group having a (meth)acryloyl group, a group having an epoxy (meth)acryloyl group, a group having a urethane (meth)acryloyl group, a group having a hydroxyl group, a group having a glycidyl group, a group having a vinylphenylmethyl group, a group having a styrene group, a group having an alkynyl group, a group having a carbon-carbon double bond, a group having a carbon-carbon triple bond, and groups including these groups.

[0177] "Acid dissociable group" refers to a group that cleaves in the presence of acid to generate an alkali-soluble group (e.g., a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group). The acid dissociable group is not particularly limited, but can be appropriately selected and used from those proposed in, for example, hydroxystyrene resins and (meth)acrylic resins used in chemically amplified resist compositions for KrF or ArF. Specific examples of acid dissociable groups include, for example, those described in International Publication No. 2016 / 158168.

[0178] A may have a substituent. Compounds forming the backbone of A include, for example, an alkane having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms, which may have a substituent; an alkene having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 6 carbon atoms, which may have a substituent; an alkyne having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 6 carbon atoms, which may have a substituent; and a cycloalkane having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 6 carbon atoms, which may have a substituent. Examples include cycloalkenes having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 6 carbon atoms, which may have substituents; cycloalkynes having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 6 carbon atoms, which may have substituents; arenes having 5 to 30 carbon atoms, preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and even more preferably 5 to 6 carbon atoms, which may have substituents; and combinations thereof.

[0179] Specific examples of compounds forming the backbone of A include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, icosan, triacontan, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloicosan, cyclotriacontan, adamantane, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, icosene, triacontene, benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, coronene, azulene, fluorene, and combinations thereof, which may have substituents. These may include ether bonds, ketone bonds, and ester bonds.

[0180] The substituents of the compound forming the backbone of A are not particularly limited, but examples include halogens (fluorine, chlorine, bromine), hydroxyl groups, cyano groups, nitro groups, amino groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aralkyl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkylloyloxy groups, aryloyloxy groups, and alkylsilyl groups, as well as various crosslinking groups and acid dissociating groups. From the perspective of increasing the stability and productivity of iodine-containing (meth)acrylate compounds, it is preferable that the substituents of the compound forming the backbone of A do not include hydroxyl groups.

[0181] "Bridge-forming groups" and "acid-dissociating groups" are not particularly limited, for example, the above R 2 You can use what is described in the explanation.

[0182] A, in that it can combine film defect reduction, compound stability, sensitivity, and etching resistance, n 1 It is preferable that it is a ring with 5 to 30 carbon atoms that is 0 and may have substituents, and n 1It is more preferable that it is an alicyclic hydrocarbon having 5 to 30 carbon atoms that is 0 and may have substituents, and n 1 It is more preferable that it be 0 and may be an adamantane having a substituent. Examples of ring-shaped groups include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloicosan, cyclotriacontan, and adamantane, which may contain ether bonds, ketone bonds, and ester bonds.

[0183] In addition, examples of alicyclic hydrocarbons include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloicosan, cyclotriacontan, and adamantane.

[0184] A comprises at least one acyl group. It is preferable that the acyl group be included as a substituent in the compound forming the backbone of A. The substituent may include ether bonds, ketone bonds, and ester bonds, but it is preferable to include ether bonds. Specific examples of acyl groups include a metanoyl group (formyl group), an ethanolyl group (acetyl group), a propanoyl group, a butanoyl group, a pentanoyyl group, a hexanoyl group, an octanoyl group, a decanoyl group, and a benzoyyl group. An ethanolyl group (acetyl group) and a benzoyyl group are preferred, and an ethanolyl group (acetyl group) is more preferred.

[0185] It is desirable for A to include at least one acyl group from the perspective of increasing the stability of the compound and (co)polymer. It is also desirable from the perspective of increasing the productivity of the compound and (co)polymer. When an acyl group is included as a substituent in the compound forming the backbone of A, the stability of the compound and (co)polymer is higher, the resin incorporating the compound and (co)polymer dissolves well in organic solvents, and storage stability is superior. Therefore, the number of acyl groups in the compound forming the backbone of A is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1.

[0186] n 1 It represents 0 or 1, and it is preferable that it be 1.

[0187] A, in that it can combine film defect reduction, sensitivity, and etching resistance, n 1 It is preferably an aromatic group having 5 to 30 carbon atoms that is 1 and may have substituents, and n 1 It is more preferable that it be benzene, which may have a substituent. Examples of aromatics include benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, and coronene. These may contain ether bonds, ketone bonds, and ester bonds.

[0188] A comprises at least one acyl group. Regarding the acyl group, it is as described above. n 1 In the case of 1, among the acyl groups, ethanolyl groups (acetyl groups) and benzoyyl groups are preferred, and ethanolyl groups (acetyl groups) are more preferred.

[0189] It is desirable for A to include at least one acyl group from the perspective of increasing the stability of the compound and (co)polymer. It is also desirable from the perspective of increasing the productivity of the compound and (co)polymer. When the acyl group is included as an aromatic substituent, the stability of the compound and (co)polymer is higher, the resin containing the compound and (co)polymer dissolves well in organic solvents, and storage stability is better. Therefore, the number of acyl groups among the aromatic substituents is preferably 1 to 8, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1.

[0190] n 2 The value is an integer from 1 to 20, and in terms of combining sensitivity and etching resistance, it is preferably an integer from 1 to 20, more preferably an integer from 1 to 10, and even more preferably an integer from 2 to 5.

[0191] The compound represented by the above formula (1) is preferably a compound represented by the following formula (2) in terms of ease of reactivity.

[0192] [Chemical Formula 16]

[0193]

[0194] In equation (2), R 1 , A, and n 2 is as defined in the above equation (1).

[0195] The compound represented by the above formula (1) is more preferably the compound represented by the following formula (3) in terms of etching resistance.

[0196] [Chemical Formula 17]

[0197]

[0198] In formula (3), B represents an organic group having 5 to 30 carbon atoms including an aromatic group, and B includes at least one acyl group. R 1 , and n 2is as defined in the above equation (1).

[0199] B may have a substituent. Examples of compounds that form the backbone of B include arenes having 5 to 30 carbon atoms, preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and even more preferably 5 to 6 carbon atoms, which may have a substituent.

[0200] Specific examples of compounds forming the backbone of B include benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, coronene, azulene, fluorene, and combinations thereof, which may have substituents. These may include ether bonds, ketone bonds, and ester bonds.

[0201] The substituents of the compound forming the backbone of B are not particularly limited, but examples include halogens (fluorine, chlorine, bromine), hydroxyl groups, cyano groups, nitro groups, amino groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aralkyl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkylloyloxy groups, aryloyloxy groups, and alkylsilyl groups, as well as various crosslinking groups and acid dissociating groups. From the perspective of increasing the stability and productivity of iodine-containing (meth)acrylate compounds, it is preferable that the substituents of the compound forming the backbone of B do not include hydroxyl groups.

[0202] "Bridge-forming groups" and "acid-dissociating groups" are not particularly limited, for example, the above R 2 The one described in the description may be used. It is preferable that the acid-dissociating group bonded to the aromatic group of B is a group that cleaves in the presence of acid to produce a hydroxyl group.

[0203] B is preferably an aromatic having 5 to 30 carbon atoms that may have substituents, in order to combine film defect reduction, sensitivity, and etching resistance, and is more preferably a benzene that may have substituents. Examples of aromatics include benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, and coronene.

[0204] B includes at least one acyl group. The acyl group is as described above. Among these, an ethanolyl group (acetyl group) and a benzoyl group are preferred, and an ethanolyl group (acetyl group) is more preferred.

[0205] It is desirable for B to include at least one acyl group from the perspective of increasing the stability of the compound and (co)polymer. It is also desirable from the perspective of increasing the productivity of the compound and (co)polymer. When an acyl group is included as a substituent in the compound forming the backbone of B, the stability of the compound and (co)polymer is higher, the resin incorporating the compound and (co)polymer dissolves well in organic solvents, and storage stability is superior. Therefore, the number of acyl groups in the compound forming the backbone of B is preferably 1 to 8, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1.

[0206] The compound represented by the above formula (1) is more preferably the compound represented by the following formula (3') in terms of etching resistance.

[0207] [Chemical Formula 18]

[0208]

[0209] In formula (3'), B' represents an organic group having 5 to 30 carbon atoms including a ring, and B' includes at least one acyl group. R 1 , and n 2 is as defined in the above equation (1).

[0210] B' may have a substituent. Examples of compounds that form the backbone of B' include, for instance, a cycloalkane having 5 to 30 carbon atoms, preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and even more preferably 5 to 6 carbon atoms, which may have a substituent; a cycloalkene having 5 to 30 carbon atoms, preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and even more preferably 5 to 6 carbon atoms, which may have a substituent; a cycloalkyne having 5 to 30 carbon atoms, preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and even more preferably 5 to 6 carbon atoms, which may have a substituent; or combinations thereof.

[0211] Specific examples of compounds that form the backbone of B' include cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloicosan, cyclotriacontan, adamantan, and combinations thereof, which may have substituents. These may include ether bonds, ketone bonds, and ester bonds.

[0212] The substituents of the compound forming the backbone of B' are not particularly limited, but examples include halogens (fluorine, chlorine, bromine), hydroxyl groups, cyano groups, nitro groups, amino groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aralkyl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkylloyloxy groups, aryloyloxy groups, and alkylsilyl groups, various crosslinking groups, and acid dissociating groups. From the perspective of increasing the stability and productivity of iodine-containing (meth)acrylate compounds, it is preferable that the substituents of the compound forming the backbone of B' do not include hydroxyl groups.

[0213] "Bridge-forming groups" and "acid-dissociating groups" are not particularly limited, for example, the above R 2You can use what is described in the explanation.

[0214] B' is preferably a cyclic aliquot having 5 to 30 carbon atoms that may have substituents, in that it can combine film defect reduction, compound stability, sensitivity, and etching resistance; it is more preferably a cyclic hydrocarbon having 5 to 30 carbon atoms that may have substituents; and it is even more preferably an adamantane that may have substituents. The aliquot and cyclic hydrocarbon are as described above.

[0215] B' includes at least one acyl group. The acyl group is as described above. Among these, an ethanolyl group (acetyl group) and a benzoyl group are preferred, and an ethanolyl group (acetyl group) is more preferred.

[0216] It is desirable for B' to include at least one acyl group from the perspective of increasing the stability of the compound and (co)polymer. It is also desirable from the perspective of increasing the productivity of the compound and (co)polymer. When an acyl group is included as a substituent in the compound forming the backbone of B', the stability of the compound and (co)polymer is higher, the resin incorporating the compound and (co)polymer dissolves well in organic solvents, and storage stability is superior. Therefore, the number of acyl groups in the compound forming the backbone of B' is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1.

[0217] Specific examples of the iodine-containing (meth)acrylate compounds of the present embodiment are provided below, but are not limited thereto. In addition, among the examples below, R 1 It represents silver, a hydrogen atom, a methyl group, or a halogen. R' represents an acyl group, preferably an acetyl group. In the examples below, I represents an iodine atom, and I 1-9 This means that 1 to 9 atoms of I are bonded to the carbons of adamantane.

[0218] [Chemical Formula 19]

[0219]

[0220] [Chemical Formula 20]

[0221]

[0222] With respect to the structural formulas described in this specification, for example, as follows, if a line indicating a connection with C is in contact with ring A and ring B, it means that C may be connected to either ring A or ring B.

[0223] [Chemical Formula 21]

[0224]

[0225] [Method for preparing iodine-containing (meth)acrylate compounds]

[0226] The iodine-containing (meth)acrylate compound of the present embodiment can be prepared according to known methods. Such methods are not particularly limited, but examples include a method of reacting an iodine-containing hydroxy compound represented by formula (a) with a (meth)acrylic acid compound represented by formula (b) to obtain an iodine-containing hydroxy(meth)acrylic acid compound, and then reacting the hydroxyl group derived from the iodine-containing hydroxy compound represented by formula (a) in the compound with an acylating agent to obtain a reaction product, and then reacting the reaction product with a (meth)acrylic acid compound represented by formula (b).

[0227] [Chemical Formula 22]

[0228]

[0229] In formula (a), A' represents an organic group having 1 to 30 carbon atoms, A' has at least one hydroxyl group, and R 2 , n 1 , and n 2...is as defined in the above formula (1). In addition, A' is identical to A of the above formula (1), except that instead of including an acyl group, it includes at least one hydroxyl group. When a hydroxyl group is included as a substituent in the compound forming the backbone of A', the stability of the compound and (co)polymer is higher, the resin incorporating the compound and (co)polymer dissolves well in organic solvents, and storage stability is superior. Therefore, the number of hydroxyl groups in the compound forming the backbone of A' is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1. The compound forming the backbone of A' is identical to the compound forming the backbone of A above.

[0230] n 2 is an integer from 1 to 20. In terms of being able to combine high sensitivity and resolution, n 2 is preferably an integer from 1 to 20, more preferably an integer from 1 to 10, and even more preferably an integer from 2 to 5.

[0231] [Chemical Formula 23]

[0232]

[0233] In Equation (b), R 1 is as defined in the above equation (1). Also, R B Is , It is a hydroxyl group, halogen, (meth)acryloyloxy group, or alkoxy group. R B Is , Halogens and (meth)acryloyloxy groups are preferred. As a halogen, chlorine is preferred. Examples of alkoxy groups include methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, n-butoxy groups, isobutoxy groups, tert-butoxy groups, n-hexanox groups, 2-methylpropoxy groups, methoxy groups, and phenoxy groups.

[0234] Equation (a) is capable of combining film defect reduction, compound stability, sensitivity, and etching resistance, in that n 1 It is a ring having 5 to 30 carbon atoms, wherein A' may have a substituent, and it is preferable that A' has at least one hydroxyl group, and n 1 It is an alicyclic hydrocarbon having 5 to 30 carbon atoms, wherein A' may have a substituent, and it is more preferable that A' has at least one hydroxyl group, and n 1 It is an adamantane in which A' may have a substituent, and it is more preferable that A' has at least one hydroxyl group. As for the alicyclic and alicyclic hydrocarbons, they are as described above.

[0235] In addition, A' is capable of combining film defect reduction, sensitivity, and etching resistance, n 1 It is an aromatic group having 5 to 30 carbon atoms, wherein A' may have a substituent, and it is preferable that A' has at least one hydroxyl group, and n 1 This is 1, and it is a benzene that may have a substituent, and it is more preferable that A' has at least one hydroxyl group. As for the aromatic group, it is as described above.

[0236] The compound represented by the above formula (a) is preferably the compound represented by the formula (a1) in that it can combine film defect reduction, compound stability, sensitivity, and etching resistance.

[0237] [Chemical Formula 24]

[0238]

[0239] In equation (a1), A', and n 2 is as above.

[0240] The compound represented by the above formula (a) is preferably the compound represented by the formula (a2) in that it can combine film defect reduction, sensitivity, and etching resistance.

[0241] [Chemical Formula 25]

[0242]

[0243] In formula (a2), B'' represents an organic group having 5 to 30 carbon atoms including an aromatic group, B'' has at least one hydroxyl group, and n 2 ...is as defined in the above formula (1). Also, B'' is identical to B of the above formula (3), except that it does not include an acyl group but instead includes at least one hydroxyl group. When the hydroxyl group is included as a substituent in the compound forming the backbone of B'', the stability of the compound and (co)polymer is higher, the resin incorporating the compound and (co)polymer dissolves well in organic solvents, and the storage stability is better. Therefore, the number of hydroxyl groups in the compound forming the backbone of B'' is preferably 1 to 8, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1. The compound forming the backbone of B'' is identical to the compound forming the backbone of B above.

[0244] Formula (a2) is an aromatic having 5 to 30 carbon atoms in which B'' may have a substituent, in order to combine film defect reduction, sensitivity, and etching resistance, and it is preferable that B'' has at least one hydroxyl group, and more preferable that B'' has at least one hydroxyl group, and is a benzene in which B'' may have a substituent. As for the aromatic, it is as described above.

[0245] The compound represented by the above formula (a) is preferably the compound represented by the formula (a3) ​​in that it can combine film defect reduction, compound stability, sensitivity, and etching resistance.

[0246] [Chemical Formula 26]

[0247]

[0248] In formula (a3), B''' represents an organic group having 5 to 30 carbon atoms containing a ring, and B''' has at least one hydroxyl group, and n 2 ...is as defined in the above formula (1). Also, B''' is identical to B' of the above formula (3'), except that it does not include an acyl group in B' of the above formula (3') and instead includes at least one hydroxyl group. When the hydroxyl group is included as a substituent in the compound forming the backbone of B''', the stability of the compound and (co)polymer is higher, the resin incorporating the compound and (co)polymer dissolves well in organic solvents, and storage stability is better; therefore, the number of hydroxyl groups in the compound forming the backbone of B''' is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1. The compound forming the backbone of B''' is identical to the compound forming the backbone of B' above.

[0249] Formula (a3) ​​is preferably a cyclic alicyclic having 5 to 30 carbon atoms that may have a substituent, and it is more preferable that B''' has at least one hydroxyl group, and B'''' has at least one hydroxyl group, and B'''' has at least one hydroxyl group, and B'''' has at least one hydroxyl group, and B'''' has at least one hydroxyl group, and B'''' has at least one hydroxyl group, and it is even more preferable that B'''' has at least one hydroxyl group, and B'''' has at least one hydroxyl group. The alicyclic alicyclic alicyclic hydrocarbons are as described above.

[0250] Specific examples of the (meth)acrylic acid compound represented by formula (b) of the present embodiment are provided below, but are not limited thereto. In addition, among the examples below, R 1 It represents silver, a hydrogen atom, a methyl group, or a halogen. R 1 It may be the same or different.

[0251] [Chemical Formula 27]

[0252]

[0253] <Method for preparing an iodine-containing hydroxy compound represented by formula (a)>

[0254] Next, a method for preparing an iodine-containing hydroxy compound represented by formula (a) will be described.

[0255] Examples of the preparation of the iodine-containing hydroxyl compound represented by formula (a) are not particularly limited, but can be prepared by performing an iodide introduction reaction on the compound of formula (Sa1) or (Sa2). When performing an iodide introduction reaction on the compound of formula (Sa2), the process of converting the iodide into the compound of formula (a) is additionally included.

[0256] In addition, in this embodiment, an iodide-introduced product in which iodine has been introduced to the compound of formula (Sa2) in advance may be used. Examples of such iodide-introduced products include 3,5-diiodosalicylicaldehyde and 4-hydroxy-3,5-diiodobenzaldehyde. An example of a process for converting to the compound of formula (a) is a reduction process.

[0257] [Chemical Formula 28]

[0258]

[0259] In formula (Sa1), R 2 , A', n 1 , and n 2The above is as described above. X can be selected from a hydroxyl group; an aliphatic or aromatic group having 1 to 30 carbon atoms having at least one selected from the group consisting of a hydroxyl group, an aldehyde group, and a carboxyl group; and a halogen (F, Cl, and Br, etc.). Examples of compounds of formula (Sa1) include salicyl alcohol, 4-hydroxybenzyl alcohol, salicylic acid, 4-hydroxyanoxic acid, 1,3,5-adamantantriol, 1,3-adamantandiol, 1-adamantanol, and 2-adamantanol.

[0260] [Chemical Formula 29]

[0261]

[0262] In equation (Sa2), A', and n 2 The above is as described above. X is as defined in formula (Sa1). E is a hydrocarbon group having 1 to 30 carbon atoms having at least one selected from the group consisting of a hydroxyl group, an aldehyde group, a carboxyl group, an ether group, a thiol group, and an amino group. Examples of compounds of formula (Sa2) include salicylaldehyde and 4-hydroxybenzaldehyde.

[0263] For iodination reactions, the Sandmeyer method; the Halex method; iodination by an iodizing agent or a compound serving as an iodine source; iodination by an iodizing agent or a compound serving as an iodine source and an oxidizing agent; iodination by an iodizing agent or a compound serving as an iodine source and a radical generator; iodination by an iodizing agent or a compound serving as an iodine source and a system in which catalytic activity is enhanced by a zeolite, etc.; and methods of performing iodination by substitution reaction with functional groups such as hydroxyl groups or halogen groups may be appropriately utilized.

[0264] As iodizing agents, known compounds serving as sources of iodine, such as iodine, potassium iodide, hydrogen iodide (HI), iodine chloride, and N-iodosuccinimide, may be suitably used. These iodizing agents are used either alone or in combination of two or more types.

[0265] In addition, known oxidizing agents such as hydrogen peroxide, iodic acid, periodic acid, and sulfuric acid may be used as oxidizing agents. These oxidizing agents are used either alone or in combination of two or more.

[0266] Method for preparing iodine-containing hydroxy(meth)acrylic acid compounds

[0267] Next, a method for preparing an iodine-containing hydroxy(meth)acrylic acid compound will be described.

[0268] The iodine-containing hydroxy compound represented by formula (a) is used in an amount of, for example, 0.5 to 100 molar equivalents, preferably 1 to 20 molar equivalents, and more preferably 1.2 to 5 molar equivalents with respect to the (meth)acrylic acid compound represented by formula (b). Within this range, the reaction proceeds sufficiently, and the yield of the iodine-containing hydroxy(meth)acrylic acid compound, which is the target product, is high, which is desirable.

[0269] As the solvent used for this reaction, generally available solvents may be used. For example, alcohols, ethers, hydrocarbons, aromatic solvents, and halogenated solvents may be appropriately used within a range that does not inhibit the reaction. Within a range that does not inhibit the reaction, a mixture of multiple solvents may also be used. Since water inhibits the reaction, the use of a dehydrating solvent is preferred. Examples of solvents include those described in this specification.

[0270] As for such solvents, it is desirable to use solvents with good solubility for the purpose of improving material stability or process efficiency regarding obtaining the final compound from the reaction. As for preferred solvents, γP and γH in the Hansen Solubility Parameters (Hansen Solubility Parameters: A User's Handbook, CRC Press, Boca Raton FL, 2007) can be used as indicators, and γP and γH can be determined from the compound structure. It is preferable for γP and γH to be low, and it is preferable for the γP value to be 6 or less, more preferable for 4 or less, and even more preferable for 2 or less. It is preferable for the γH value to be 6 or less, more preferable for 4 or less, and even more preferable for 2 or less. Such solvents include aromatic solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, and octane; It is preferable to use halogenated solvents such as dichloromethane, dichloroethane, and chloroform as the main solvent.

[0271] The reaction temperature and reaction time depend on the substrate concentration or the catalyst used, but generally, the reaction temperature can be -20°C to 100°C, the reaction time 1 hour to 30 hours, and the pressure can be carried out under atmospheric pressure, reduced pressure, or increased pressure. In addition, the reaction can be carried out by appropriately selecting known methods such as batch, semi-batch, and continuous methods.

[0272] In addition, polymerization inhibitors may be added to the series of reactions, and commercially available products may be used. Examples of such polymerization inhibitors include nitroso compounds such as 2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl, N-nitrosophenylhydroxyamine ammonium salt, N-nitrosophenylhydroxyamine aluminum salt, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, N-nitrosodiphenylamine, N-nitroso-N-methylaniline, nitrosonaphthol, p-nitrosophenol, and N,N'-dimethyl-p-nitrosoaniline; sulfur-containing compounds such as phenothiazine, methylene blue, and 2-mercaptobenzimidazole; Examples include amines such as N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, 4-hydroxydiphenylamine, and aminophenol; quinones such as hydroxyquinoline, hydroquinone, methylhydroquinone, p-benzoquinone, and hydroquinone monomethyl ether; phenols such as 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, catechol, 3-s-butylcatechol, and 2,2-methylenebis-(6-t-butyl-4-methylphenol); imides such as N-hydroxyphthalimide; oximes such as cyclohexane oxime and p-quinone dioxime; and dialkylthiodipropinates. The amount added is, for example, 0.001 to 10 parts by mass, preferably 0.01 to 1 part by mass, with respect to 100 parts by mass of the (meth)acrylic acid compound represented by formula (b).

[0273] In addition, a catalyst may be added to the series of reactions, and various catalysts that function as reaction conditions of the present embodiment are used. For example, acid catalysts or base catalysts are preferred as such catalysts.

[0274] Suitable acid catalysts include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromide, and hydrofluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; and solid acids such as silicotic acid, phosphotungtic acid, silicotic molybdic acid, and phosphomolybdic acid. These acid catalysts are used individually or in combination of two or more types. Among these, organic acids and solid acids are preferred from a manufacturing perspective, and p-toluenesulfonic acid, hydrochloric acid, and sulfuric acid are preferred from a manufacturing perspective, such as ease of availability or ease of handling.

[0275] Suitable basic catalysts include, for example, amine-containing catalysts such as pyridine and ethylenediamine; and non-amine basic catalysts such as metal salts. Potassium salts and acetates are preferred as metal salts, and examples of such catalysts include potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide, and magnesium oxide.

[0276] Non-amine base catalysts are commercially available, for example, from EM Science and Aldrich.

[0277] These catalysts are used either alone or in combination of two or more types.

[0278] The amount of catalyst used can be appropriately set according to the substrate, catalyst, and reaction conditions used, and is not particularly limited, but generally, 1 to 5,000 parts by mass per 100 parts by mass of reaction raw material is suitable, and from the perspective of yield, 50 to 3,000 parts by mass is preferable.

[0279] The iodine-containing hydroxy(meth)acrylic acid compound obtained by the reaction can be isolated and purified using known purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and separation and purification methods using activated carbon, or a combination thereof, to obtain a desired high-purity monomer. Furthermore, for the purpose of removing metal-containing impurities such as metal ions and metal oxides contained in the obtained high-purity monomer, a purification method for removing metal impurities described below may be added. The high-purity monomer obtained has a content of various metals (e.g., sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), iron (Fe), copper (Cu), nickel (Ni), tin (Sn), silver (Ag), molybdenum (Mo), manganese (Mn), zinc (Zn), cobalt (Co), aluminum (Al), lead (Pb), chromium (Cr), and titanium (Ti)) included in the compound that is typically 10 ppb or less, preferably 5 ppb or less, and more preferably 1 ppb or less.

[0280] In addition, iodine-containing hydroxy(meth)acrylic acid compounds can be acylated as is without isolation and purification.

[0281] A purification method for the purpose of removing metal impurities is not particularly limited, but comprises a process of dissolving an iodine-containing hydroxy(meth)acrylic acid compound in a solvent to obtain a solution (S), and a process of contacting the solution (S) with an acidic aqueous solution to extract impurities from the iodine-containing hydroxy(meth)acrylic acid compound (hereinafter also referred to as “compound (A)”) (first extraction process), wherein the solvent used in the process of obtaining the solution (S) comprises an organic solvent that is not miscible with water.

[0282] According to this purification method, the content of various metals included as impurities in compound (A) can be reduced.

[0283] More specifically, a compound (A) can be dissolved in an organic solvent that is not miscible with water to obtain a solution (S), and then the solution (S) can be brought into contact with an acidic aqueous solution to perform an extraction treatment. Accordingly, the extracted metal component contained in the solution (S) is transferred to the aqueous phase, and then the organic phase and the aqueous phase are separated to obtain a compound (A) with a reduced metal content.

[0284] The solvent used in the above purification method that is not miscible with water is not particularly limited, but it is preferably an organic solvent that can be safely applied to a semiconductor manufacturing process. Specifically, it is preferably an organic solvent with a solubility in water of less than 30% at room temperature (25°C), more preferably less than 20%, and even more preferably less than 10%. The amount of organic solvent used is preferably 1 to 100 times by mass relative to the total amount of compound (A) used.

[0285] Specific examples of solvents that are not miscible with water include, for example, ethers such as diethyl ether and diisopropyl ether; esters such as ethyl acetate, n-butyl acetate, and isoamyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 2-pentanone; glycol ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; aromatic hydrocarbons such as toluene and xylene; and halogenated hydrocarbons such as methylene chloride and chloroform. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, and ethyl acetate are preferred, methyl isobutyl ketone, ethyl acetate, cyclohexanone, and propylene glycol monomethyl ether acetate are more preferred, and methyl isobutyl ketone and ethyl acetate are even more preferred. Since methyl isobutyl ketone and ethyl acetate have a relatively high saturated solubility of compound (A) and a relatively low boiling point, it is possible to reduce the load in the process of industrially removing solvents and removing them by drying. These solvents are used either alone or in combination of two or more types.

[0286] The acidic aqueous solution used in the above purification method is suitably selected from acidic aqueous solutions in which a generally known organic or inorganic compound is dissolved in water. Examples of such aqueous solutions include an aqueous solution of an inorganic acid in which an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid is dissolved in water; an aqueous solution of an organic acid in which a polycarboxylic acid such as acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, and citric acid, or an organic acid such as methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid is dissolved in water. These acidic aqueous solutions are used either alone or in combination of two or more. Among these acidic aqueous solutions, aqueous solutions of sulfuric acid, nitric acid, and acetic acid, as well as polycarboxylic acids such as oxalic acid, tartaric acid, and citric acid, are preferred; aqueous solutions of sulfuric acid, oxalic acid, tartaric acid, and citric acid are more preferred; and aqueous solutions of oxalic acid are even more preferred. Polycarboxylic acids such as oxalic acid, tartaric acid, and citric acid coordinate with metal ions and generate a chelating effect, so it is thought that they tend to be able to remove metals more effectively. Furthermore, regarding the water used here, depending on the purpose of the purification method in this embodiment, it is preferable to use water with a low metal content, for example, ion-exchanged water.

[0287] The pH of the acidic aqueous solution used in the above purification method is not particularly limited, but it is desirable to adjust the acidity of the aqueous solution considering the effect on compound (A). Typically, the pH range is about 0 to 5, and preferably about 0 to 3.

[0288] The amount of acidic aqueous solution used in the above purification method is not particularly limited, but it is desirable to adjust the amount in order to reduce the number of extractions for metal removal and to ensure operability by considering the total amount of liquid. In this regard, the amount of acidic aqueous solution used is preferably 10 to 200 mass% and more preferably 20 to 100 mass% with respect to 100 mass% of solution (S).

[0289] In the above purification method, metal components can be extracted from a compound (A) in the solution (S) by contacting the acidic aqueous solution with the solution (S).

[0290] In the above purification method, the solution (S) may additionally include an organic solvent that is optionally miscible with water. When an organic solvent that is optionally miscible with water is included, the amount of compound (A) added can be increased, and furthermore, the separation properties are improved, and purification can be performed with high pot efficiency. Methods for adding an organic solvent that is optionally miscible with water include, for example, adding it to a solution containing the organic solvent beforehand, adding it to water or an acidic aqueous solution beforehand, and adding it after contacting the solution containing the organic solvent with water or an acidic aqueous solution. Among these, the method of adding it to a solution containing the organic solvent beforehand is preferred in terms of operational efficiency and ease of managing the amount added.

[0291] The organic solvent that is optionally miscible with water used in the above purification method is not particularly limited, but an organic solvent that can be safely applied to a semiconductor manufacturing process is preferred. The amount of organic solvent that is optionally miscible with water is not particularly limited as long as it is within a range where the solvent phase and the aqueous phase are separated, but it is preferable that it is 0.1 to 100 times by mass with respect to the total amount of compound (A), more preferable that it is 0.1 to 50 times by mass, and even more preferable that it is 0.1 to 20 times by mass.

[0292] Organic solvents that are optionally miscible with water used in the above purification method may include, for example, ethers such as tetrahydrofuran and 1,3-dioxolane; alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone and N-methylpyrrolidone; and aliphatic hydrocarbons such as glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and propylene glycol monoethyl ether. Among these, N-methylpyrrolidone and propylene glycol monomethyl ether are preferred. These solvents are used either alone or in combination of two or more types.

[0293] The temperature at which the extraction treatment is performed is not particularly limited, but is typically 20 to 90°C, preferably in the range of 30 to 80°C. The extraction operation is performed by thoroughly mixing, for example, by stirring, to obtain a mixed solution, and then allowing this mixed solution to stand. Accordingly, the metal components contained in the solution (S) are transferred to the aqueous phase. In addition, through this operation, the acidity of the solution is lowered, which can suppress the deterioration of the compound (A).

[0294] The above mixed solution is separated into a solvent phase containing compound (A) and a solvent and an aqueous phase by settling, and the solvent phase is recovered by decanting, etc. The settling time is not particularly limited, but it is desirable to adjust the settling time from the perspective of better separation of the solvent phase and the aqueous phase. Typically, the settling time is 1 minute or more, preferably 10 minutes or more, and more preferably 30 minutes or more. In addition, the extraction treatment may be performed only once, but it is also effective to repeat the operations of mixing, settling, and separation multiple times.

[0295] In the above purification method, it is preferable to include a process (second extraction process) in which, after the first extraction process, the solvent phase containing compound (A) is further brought into contact with water to extract impurities in compound (A). Specifically, for example, it is preferable to perform the extraction treatment using an acidic aqueous solution, recover the aqueous solution, and then provide the remaining solvent phase containing compound (A) and solvent to further extract the solution with water. The extraction treatment by the second extraction process is not particularly limited, but can be performed, for example, by thoroughly mixing the solvent phase and water by stirring, and then allowing the obtained mixed solution to stand. Since the mixed solution after standing is separated into a solvent phase containing compound (A) and solvent and an aqueous phase, the solvent phase can be recovered by decanting, etc.

[0296] In addition, the water used here is preferably water with a low metal content, such as ion-exchanged water, depending on the purpose of the present embodiment. The extraction treatment may be performed only once, but it is also effective to repeat the operations of mixing, settling, and separation multiple times. Furthermore, the usage ratio of the two materials, temperature, and time conditions in the extraction treatment are not particularly limited, and the above may be used as a reference.

[0297] Water that may be incorporated into the solution containing the compound (A) obtained in this manner and the solvent can be easily removed by performing operations such as vacuum distillation. Additionally, if necessary, a solvent can be added to the solution to adjust the concentration of the compound (A) to any desired concentration.

[0298] A method for purifying compound (A) may be performed by passing a solution in which compound (A) is dissolved in a solvent through a filter.

[0299] According to the purification method of the present embodiment, the content of various metal components in compound (A) can be effectively and significantly reduced.

[0300] Meanwhile, in the present embodiment, "flow" means that the solution moves from the outside of the filter, through the inside of the filter, and then back to the outside of the filter. For example, the case where the solution is simply brought into contact with the surface of the filter, or the case where the solution is brought into contact with the surface while moving from the outside of the ion exchange resin (i.e., the case where it is simply brought into contact) are excluded.

[0301] The purification method using a filter is described in detail.

[0302] As for the filter, commercially available filters for liquid filtration may be used. The filtration precision of the filter is not particularly limited, but the nominal pore diameter of the filter is preferably 0.2 μm or less, more preferably less than 0.2 μm, even more preferably 0.1 μm or less, even more preferably less than 0.1 μm, and even more preferably 0.05 μm or less. In addition, the lower limit of the nominal pore diameter of the filter is not particularly limited, but is typically 0.005 μm. The nominal pore diameter referred to here is the nominal hole diameter indicating the separation performance of the filter, and is a hole diameter determined according to test methods specified by the filter manufacturer, such as the bubble point test, mercury intrusion test, and standard particle supplementation test. When using a commercially available product, it is the value listed in the manufacturer's catalog data. By making the nominal pore size 0.2 μm or less, the content of metal particles after passing the solution through the filter once can be effectively reduced. To further reduce the content of each metal particle in the solution, the solution may be passed through the filter two or more times.

[0303] As for the form of the filter, hollow fiber membrane filters, membrane filters, pleated membrane filters, and filters filled with filter media such as nonwoven fabric, cellulose, and diatomaceous earth may be used. Among the above, it is preferable that the filter be one or more types selected from the group consisting of hollow fiber membrane filters, membrane filters, and pleated membrane filters. Furthermore, it is more preferable to use a hollow fiber membrane filter due to its particularly high filtration precision and the height of the filtration area compared to other types.

[0304] Examples of materials for the above filter include polyolefins such as polyethylene and polypropylene; polyethylene-based resins having functional groups capable of ion exchange through graft polymerization; polar group-containing resins such as polyamide, polyester, and polyacrylonitrile; and fluorine-containing resins such as fluorinated polyethylene (PTFE). Among these, it is preferable that the filter material be one or more selected from the group consisting of polyamide, polyolefin, and fluorine resin. Furthermore, polyamide is more preferable in that it can further reduce heavy metals such as chromium. On the other hand, from the perspective of avoiding metal leaching from the material, it is preferable to use a filter other than a sintered metal material.

[0305] Examples of polyamide-based filters include the Polyfix (registered trademark) Nylon series manufactured by Kits Microfilter Co., Ltd., Ultipleats (registered trademark) P-Nylon 66 and Ultipore (registered trademark) N66 manufactured by Nippon Pole Co., Ltd., and the Life Assure (registered trademark) PSN series and Life Assure (registered trademark) EF series manufactured by 3M.

[0306] Examples of polyolefin-based filters include Ultiplets (registered trademark) PE Clean and Ion Clean manufactured by Nippon Pol Co., Ltd., Protego (registered trademark) series manufactured by Nippon Integrys Co., Ltd., Microguard (registered trademark) Plus HC10, and Optimizer D.

[0307] Examples of polyester-based filters include the Zeraflow DFE manufactured by Central Filter Industry Co., Ltd. and the pleated type (registered trademark) PMC manufactured by Nippon Filter Co., Ltd.

[0308] Examples of polyacrylonitrile-based filters include the Ultra Filter AIP-0013D, ACP-0013D, and ACP-0053D manufactured by Advantech Toyo Co., Ltd.

[0309] Examples of fluoropolymer-based filters include the Amplon (registered trademark) HTPFR manufactured by Nippon Pol Co., Ltd. and the LifeAssure FA series manufactured by 3M.

[0310] These filters are used either individually or in combination of two or more types.

[0311] In addition, the filter may contain an ion exchanger such as a cation exchange resin, or a cation charge regulator that generates a zeta potential in the organic solvent solution being filtered.

[0312] Examples of filters containing ion exchangers include the Protego (registered trademark) series manufactured by Japan Integrys Co., Ltd. and the Kurangraft (registered trademark) manufactured by Kurashiki Textile Co., Ltd.

[0313] In addition, filters containing materials having a positive zeta potential, such as polyamide polyamine epichlorohydrin cation resin, include, for example, 3M Zeta Plus (registered trademark) 40QSH, Zeta Plus (registered trademark) 020GN, and Life Assure (registered trademark) EF series.

[0314] The method of isolating compound (A) from a solution containing compound (A) and a solvent is not particularly limited and can be carried out by known methods such as depressurization, separation by re-precipitation, and combinations thereof. If necessary, known treatments such as concentration, filtration, centrifugation, and drying may be performed.

[0315] Method for preparing iodine-containing (meth)acrylate compounds

[0316] Next, a method for manufacturing the iodine-containing (meth)acrylate compound of the present embodiment will be described.

[0317] Iodine-containing (meth)acrylate compounds can be obtained by reacting the hydroxyl groups in iodine-containing hydroxy(meth)acrylic acid compounds with an acylating agent. Suitable acylating agents are not particularly limited, but examples include acetic anhydride, acetyl halides, and acetic acid. Among these, acetic anhydride is preferred.

[0318] This reaction may be carried out in an organic solvent. As the organic solvent, a wide variety of organic solvents are used, including polar aprotic organic solvents and protonic polar organic solvents. A single protonic polar solvent or a single polar aprotic solvent may be used. Furthermore, a mixture of polar aprotic solvents, a mixture of protonic polar solvents, a mixture of polar aprotic solvents and protonic polar solvents, and a mixture of aprotic or protonic solvents and nonpolar solvents may be used. Among these, a polar aprotic solvent or a mixture thereof is preferred.

[0319] The solvent is effective but not an essential component. Suitable polar aprotic solvents include, for example, alcohol-based solvents such as methanol and ethanol; ether-based solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, deglaim, and triglaim; ester-based solvents such as ethyl acetate and γ-butyrolactone; nitrile-based solvents such as acetonitrile; hydrocarbon-based solvents such as toluene and hexane; amide-based solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphorate triamide; and dimethyl sulfoxide. Among these, toluene and dimethyl sulfoxide are preferred. Suitable protonite polar solvents include, for example, di(propylene glycol)methyl ether, di(ethylene glycol)methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol.

[0320] The amount of solvent used can be appropriately set according to the substrate, catalyst, and reaction conditions used, and is not particularly limited, but generally, 0 to 10,000 parts by mass per 100 parts by mass of reaction raw material is suitable, and from the perspective of yield, 100 to 2,000 parts by mass is preferable.

[0321] A catalyst may be used in this reaction. As the catalyst, various acylation catalysts that function under the reaction conditions of the present embodiment are used, and acid catalysts or base catalysts are preferred.

[0322] Suitable acid catalysts include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromide, and hydrofluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; and solid acids such as silicotic acid, phosphotungtic acid, silicotic molybdic acid, and phosphomolybdic acid. These acid catalysts are used individually or in combination of two or more types. Among these, organic acids and solid acids are preferred from a manufacturing perspective, and hydrochloric acid or sulfuric acid is more preferred from a manufacturing perspective, such as ease of availability or ease of handling.

[0323] Suitable basic catalysts include, for example, amine-containing catalysts such as pyridine and ethylenediamine; and non-amine basic catalysts such as metal salts. Potassium salts and acetates are preferred as metal salts. Examples of such catalysts include potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide, and magnesium oxide.

[0324] Non-amine base catalysts are commercially available, for example, from EM Science and Aldrich.

[0325] These catalysts are used either alone or in combination of two or more types.

[0326] The amount of catalyst used can be appropriately set according to the substrate, catalyst, and reaction conditions used, and is not particularly limited, but generally, 1 to 5,000 parts by mass per 100 parts by mass of reaction raw material is suitable, and from the perspective of yield, 50 to 3,000 parts by mass is preferable.

[0327] A polymerization inhibitor may be used in this reaction. As the polymerization inhibitor, various polymerization inhibitors that function as reaction conditions of the present embodiment are used. The polymerization inhibitor is effective but is not an essential component. Suitable polymerization inhibitors include, in addition to those described herein, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, phenothiazine, N-oxyl (nitroxide) inhibitors (e.g., Prostab (registered trademark) 5415 (bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate marketed by Ciba Specialty Chemicals), 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-yloxy marketed by Tokyo Kasei Kogyo Inc.), and Uvinul (registered trademark) 4040P (marketed by BASF Examples include 1,6-hexamethylene-bis(N-formyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)amine). These polymerization inhibitors are used either alone or in combination of two or more.

[0328] The amount of polymerization inhibitor used can be appropriately set according to the substrate, catalyst, and reaction conditions used, and is not particularly limited, but generally, 0.0001 to 100 parts by mass per 100 parts by mass of reaction raw material is suitable, and from the perspective of yield, 0.001 to 10 parts by mass is preferable.

[0329] A polymerization inhibitor may be used in this reaction. Various polymerization inhibitors that function as reaction conditions of the present embodiment are used as polymerization inhibitors. The polymerization inhibitor is effective but is not an essential component. Examples of polymerization inhibitors include hydroquinone, methoquinone, methoxyphenol, hydroxyanisole, di-t-butylhydroquinone, toluhydroquinone, butylhydroquinone, benzoquinone, methyl-p-benzoquinone, toluquinone, butyl-p-benzoquinone, and diphenyl-p-benzoquinone. These polymerization inhibitors are used either alone or in combination of two or more.

[0330] In addition, it is effective to use polymerization retardants in combination with polymerization inhibitors. Polymerization retardants are well known in the art and are compounds that slow down the polymerization reaction but cannot prevent the polymerization entirely. Common polymerization retardants are aromatic nitro compounds such as dinitro-ortho-cresol (DNOC) and dinitrobutylphenol (DNBP). Methods for manufacturing polymerization retardants are common and well known in the art (e.g., U.S. Patent No. 6,339,177; see Park et al., Polymer (Korea) (1988), 12(8), 710-19), and their use in controlling styrene polymerization is well documented (e.g., see Bushby et al., Polymer (1998), 39(22), 5567-5571). These polymerization retardants are used individually or in combination of two or more types.

[0331] The amount of polymerization inhibitor used can be appropriately set according to the substrate, catalyst, and reaction conditions used, and is not particularly limited, but generally, 0.0001 to 100 parts by mass per 100 parts by mass of reaction raw material is suitable, and from the perspective of yield, 0.001 to 10 parts by mass is preferable.

[0332] The reaction is carried out by adding an iodine-containing hydroxy(meth)acrylic acid compound, an acylating agent, and, if necessary, an organic solvent, a catalyst, a polymerization inhibitor, a polymerization inhibitor, and a polymerization retardant to a reactor to form a reaction mixture. Any suitable reactor is used for the reaction. In addition, the reaction can be carried out by appropriately selecting known methods such as batch, semi-batch, and continuous methods.

[0333] The reaction temperature is not particularly limited, as it varies depending on the concentration of the substrate, the stability of the formed product, the selection of the catalyst, and the desired yield. Generally, a temperature of 0 to 200°C is suitable, and from the perspective of yield, a temperature of 0 to 100°C is preferred.

[0334] The reaction pressure is not particularly limited, as it varies depending on the substrate concentration, the stability of the formed product, the selection of the catalyst, and the desired yield. The pressure can be controlled by using an inert gas such as nitrogen, or by using an intake pump, etc. For reactions at high pressure, a conventional pressure reactor including a shaking vessel, a rocker vessel, and a stirred autoclave is used.

[0335] The reaction time varies depending on the concentration of the substrate, the stability of the product formed, the selection of the catalyst, and the desired yield, and is not particularly limited. Typically, most reactions are carried out in less than 12 hours, and the reaction time is generally 15 to 600 minutes.

[0336] Isolation and purification can be carried out after the reaction is completed using a suitable method known in the prior art. For example, the reaction mixture is poured over ice water and extracted in an organic solvent such as ethyl acetate, butyl acetate, and diethyl ether. Subsequently, the product is recovered by removing the solvent using evaporation under reduced pressure. The iodine-containing (meth)acrylate compound can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and activated carbon, or by a combination thereof, to obtain the desired high-purity monomer. Furthermore, a purification method aimed at removing metal impurities may be added to the obtained high-purity monomer to remove metal-containing impurities such as metal ions and metal oxides. For details of the purification method, the methods described in the above and examples in this specification may be referenced. The high-purity monomer obtained has a content of various metals (e.g., Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti) included in the compound that is typically 10 ppb or less, preferably 5 ppb or less, and more preferably 1 ppb or less.

[0337] The compound of the present embodiment can be widely and effectively used, for example, in electrical insulating materials, resins for resists, encapsulating resins for semiconductors, adhesives for printed circuit boards, electrical laminates mounted on electrical equipment, electronic equipment, industrial equipment, etc., matrix resins for prepregs mounted on electrical equipment, electronic equipment, industrial equipment, etc., build-up laminate materials, resins for fiber-reinforced plastics, encapsulating resins for liquid crystal display panels, paints, various coating agents, adhesives, coating agents for semiconductors, resins for semiconductor resists, and resins for forming a resist underlayer.

[0338] [Iodine-containing (meth)acrylate (co)polymer]

[0339] Since the compound of the present embodiment has high stability, the iodine-containing (meth)acrylate (co)polymer containing this compound as a constituent unit also has high stability and can efficiently produce the (co)polymer.

[0340] In addition, by forming a (co)polymer containing the compound of the present embodiment as a constituent unit, a polymer containing one or more halogen elements, one or more hydrophilic groups, or one or more degradable groups can be formed. As a result, by a resist composition having a (co)polymer containing the compound of the present embodiment as a constituent unit as a resin component, high sensitivity in the lithography process and high resolution by expanding the solubility contrast of the resin during development can be achieved.

[0341] The (co)polymer of the present embodiment has a constituent unit represented by the following formula (4).

[0342] [Chemical Formula 30]

[0343]

[0344] In equation (4), R 1 , R 2 , A, n 1 , and n 2is as defined in the above equation (1), and the symbol * indicates a connection point with an adjacent constituent unit. n 2 The value is an integer from 1 to 20, and in terms of combining sensitivity and etching resistance, it is preferably an integer from 1 to 20, more preferably an integer from 1 to 10, and even more preferably an integer from 2 to 5.

[0345] A comprises at least one acyl group. The acyl group is as described above. Among these, an ethanolyl group (acetyl group) and a benzoyl group are preferred, and an ethanolyl group (acetyl group) is more preferred.

[0346] It is desirable for A to include at least one acyl group from the perspective of increasing the stability of the (co)polymer. It is also desirable from the perspective of increasing the productivity of the (co)polymer. When an acyl group is included as a substituent in the compound forming the backbone of A, the stability of the compound and the (co)polymer is higher, the resin incorporating the compound and the (co)polymer dissolves well in organic solvents, and the storage stability is superior. Therefore, the number of acyl groups in the compound forming the backbone of A is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1. The compound forming the backbone of A is as described above.

[0347] In a practical application, the (co)polymer may be used by hydrolyzing part or all of the acyl groups included in A to form hydroxyl groups. By having hydroxyl groups, a (co)polymer can be obtained that has superior alkali development properties and can combine reduction of film defects, compound stability, and sensitivity. The (co)polymer may include a constituent unit represented by formula (4), along with a constituent unit having a hydroxyl group obtained by hydrolyzing part or all of the acyl groups included in A in formula (4).

[0348] The (co)polymer can be obtained as a polymer (homopolymer) composed of the compounds of the present embodiment, as a copolymer obtained by polymerizing two or more compounds of the present embodiment, or as a copolymer obtained by polymerizing one or more compounds of the present embodiment and one or more other monomers. In the present embodiment, these polymers are collectively referred to as "(co)polymer." The (co)polymer can be used as a film-forming material for lithography and as a resist film-forming material, etc.

[0349] In equation (4), n in that it can combine film defect reduction, compound stability, sensitivity, and etching resistance. 1 It is preferable that this is 0, and that A is a ring with 5 to 30 carbon atoms that may have a substituent, and n 1 It is more preferable that this is 0, and that A is a carbon alicyclic hydrocarbon having 5 to 30 carbon atoms that may have a substituent, and n 1 It is more preferable that this is 0 and that A is an adamantane that may have a substituent. As for alicyclic and alicyclic hydrocarbons, they are as described above.

[0350] In addition, in the case of Equation (4), n can combine film defect reduction, sensitivity, and etching resistance. 1 It is preferable that this is 1, and that A is an aromatic group having 5 to 30 carbon atoms that may have a substituent, and n 1 It is more preferable that this be 1, and that it be benzene which may have a substituent. As for the aromatic group, it is as described above.

[0351] The (co)polymer comprises a constituent unit derived from the iodine-containing (meth)acrylate compound of the present embodiment, and a preferred embodiment of the iodine-containing (meth)acrylate compound is as described above. The (co)polymer comprises, for example, a constituent unit derived from the compound represented by Formula (1), the compound represented by Formula (2), the compound represented by Formula (3), and the compound represented by Formula (3'). Meanwhile, the constituent unit derived from the compound represented by Formula (1) corresponds to the constituent unit represented by Formula (4), and the same interpretation applies to the compound represented by Formula (2), the compound represented by Formula (3), and the compound represented by Formula (3').

[0352] Other monomers are not particularly limited, but examples include compounds (monomers) described in International Publication No. 2016 / 125782, International Publication No. 2015 / 115613, Japanese Patent Publication No. 2015-117305, International Publication No. 2014 / 175275, and Japanese Patent Publication No. 2012-162498. Additionally, the copolymer may include a constituent unit represented by formula (C1) and a constituent unit represented by formula (C2). These monomers and constituent units are used individually or in combination of two or more types.

[0353] [Chemical Formula 31]

[0354]

[0355] In Equation (C1), R C11 represents a hydrogen atom or a methyl group, and R C12 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R C13 silver, R C13 It combines with the bonding carbon atom to form a cycloalkyl or heterocycloalkyl group having 4 to 20 carbon atoms, and the symbol * indicates the bonding location with an adjacent constituent unit. R 13 It may have a substituent (e.g., an oxo group).

[0356] Preferably, R C12 represents a hydrogen atom or a C1-C3 alkyl group, and R C13 silver, R C13 It becomes one with the carbon atom that bonds to it, and is a cycloalkyl group or heterocycloalkyl group having 4 to 10 carbon atoms.

[0357] [Chemical Formula 32]

[0358]

[0359] In Equation (C2), R C21 represents a hydrogen atom or a methyl group, and R C22 and R C23 Each independently represents an alkyl group having 1 to 4 carbon atoms, and R C24 represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, and R C22 ~R C24 Two or three of them may become one with the carbon atom to which they bond to form a cyclic structure having 3 to 20 carbon atoms, and the symbol * indicates the bonding location with an adjacent constituent unit. In addition, the cyclic structure may have substituents (e.g., hydroxyl groups and alkyl groups).

[0360] Preferably, R C22 represents an alkyl group having 1 to 3 carbon atoms, and R C24 is a cycloalkyl group having 5 to 10 carbon atoms. Also, R C22 ~R C24 The above-mentioned ring structure formed by may include, for example, a plurality of rings such as adamantyl groups.

[0361] As monomer raw materials for the constituent unit represented by formula (C2), for example, 2-methyl-2-(meth)acryloyloxyadamantan (2-methyl-2-adamanthyl(meth)acrylate), 2-ethyl-2-(meth)acryloyloxyadamantan, 2-isopropyl-2-(meth)acryloyloxyadamantan, 2-n-propyl-2-(meth)acryloyloxyadamantan, 2-n-butyl-2-(meth)acryloyloxyadamantan, 3-hydroxy-1-adamanthyl(meth)acrylic acid ester, 1-methyl-1-(meth)acryloyloxycyclopentane, 1-ethyl-1-(meth)acryloyloxycyclopentane, 1-methyl-1-(meth)acryloyloxycyclohexane, Examples include 1-ethyl-1-(meth)acryloyloxycyclohexane, 1-methyl-1-(meth)acryloyloxycycloheptane, 1-ethyl-1-(meth)acryloyloxycycloheptane, 1-methyl-1-(meth)acryloyloxycyclooctane, 1-ethyl-1-(meth)acryloyloxycyclooctane, 2-ethyl-2-(meth)acryloyloxydecahydro-1,4:5,8-dimethanonaphthalene, and 2-ethyl-2-(meth)acryloyloxynobonane. Commercially available monomers may also be used.

[0362] Other constituent units besides those represented by formulas (C1) and (C2) may be constituent units derived from monomers such as γ-butyrolactone (meth)acrylic acid ester, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 3,5-diiodo-4-hydroxystyrene, and maleic anhydride. Commercially available monomers may also be used.

[0363] The iodine-containing (meth)acrylate (co)polymer represented by Formula (5), obtained using the iodine-containing (meth)acrylate compound represented by Formula (2) as a constituent unit; the iodine-containing (meth)acrylate (co)polymer represented by Formula (6), obtained using the iodine-containing (meth)acrylate compound represented by Formula (3) as a constituent unit; and the iodine-containing (meth)acrylate (co)polymer represented by Formula (6'), obtained using the iodine-containing (meth)acrylate compound represented by Formula (3') as a constituent unit, can also be obtained in the same way. The (co)polymer represented by Formula (5), the (co)polymer represented by Formula (6), and the (co)polymer represented by Formula (6') are desirable because they improve the performance of the film-forming material for lithography.

[0364] [Chemical Formula 33]

[0365]

[0366] In equation (5), R 1 , n 2 , and A are as defined in the above equation (1), and the symbol * is as defined in the above equation (4).

[0367] [Chemical Formula 34]

[0368]

[0369] In equation (6), R 1 , n 2 , and B are as defined in the above equation (3), and the symbol * is as defined in the above equation (4).

[0370] B includes at least one acyl group. The acyl group is as described above. Among these, an ethanolyl group (acetyl group) and a benzoyl group are preferred, and an ethanolyl group (acetyl group) is more preferred.

[0371] It is desirable for B to include at least one acyl group from the perspective of increasing the stability of the (co)polymer. It is also desirable from the perspective of increasing the productivity of the (co)polymer. When an acyl group is included as a substituent in the compound forming the backbone of B, the stability of the compound and the (co)polymer is higher, the resin incorporating the compound and the (co)polymer dissolves well in organic solvents, and storage stability is superior. Therefore, the number of acyl groups in the compound forming the backbone of B is preferably 1 to 8, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1.

[0372] In a practical application, the (co)polymer may be used by hydrolyzing some or all of the acyl groups included in B to form hydroxyl groups. By having hydroxyl groups, a (co)polymer can be obtained that has superior alkali development properties and can also have reduced film defects and sensitivity. The (co)polymer may include a constituent unit represented by formula (6) and a constituent unit having a hydroxyl group obtained by hydrolyzing some or all of the acyl groups included in B in formula (6).

[0373] In formula (6), B is preferably an aromatic having 5 to 30 carbon atoms that may have substituents, in order to have reduced film defects, sensitivity, and etching resistance, and is more preferably a benzene that may have substituents. As for the aromatics, they are as described above.

[0374] [Chemical Formula 35]

[0375]

[0376] In equation (6'), R 1 , n 2 , and B' are as defined in the above equation (3'), and the symbol * is as defined in the above equation (4).

[0377] B' includes at least one acyl group. The acyl group is as described above. Among these, an ethanolyl group (acetyl group) and a benzoyl group are preferred, and an ethanolyl group (acetyl group) is more preferred.

[0378] It is desirable for B' to include at least one acyl group from the perspective of increasing the stability of the (co)polymer. It is also desirable from the perspective of increasing the productivity of the (co)polymer. When an acyl group is included as a substituent in the compound forming the backbone of B', the stability of the compound and the (co)polymer is higher, the resin incorporating the compound and the (co)polymer dissolves well in organic solvents, and storage stability is superior. Therefore, the number of acyl groups in the compound forming the backbone of B' is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and even more preferably 1.

[0379] In a practical application, the (co)polymer may be used by hydrolyzing some or all of the acyl groups included in B' to form hydroxyl groups. By having hydroxyl groups, a (co)polymer can be obtained that has superior alkali development properties and can combine reduction of film defects and sensitivity. The (co)polymer may include a constituent unit represented by formula (6') and a constituent unit having a hydroxyl group obtained by hydrolyzing some or all of the acyl groups included in B' in formula (6').

[0380] In formula (6'), B' is preferably a cyclic aliquot having 5 to 30 carbon atoms that may have substituents, more preferably a cyclic hydrocarbon having 5 to 30 carbon atoms that may have substituents, and even more preferably an adamantane that may have substituents. The aliquot and cyclic hydrocarbons are as described above.

[0381] Method for manufacturing iodine-containing (meth)acrylate (co)polymer

[0382] Next, a method for manufacturing the (co)polymer of the present embodiment by polymerization reaction will be described.

[0383] The polymerization reaction is carried out by dissolving the constituent monomers in a solvent, adding a catalyst, and heating or cooling. The reaction conditions can be arbitrarily set according to the type of initiator, the initiation method such as heat and light, temperature, pressure, concentration, solvent, and additives. The preparation of the (co)polymer can be carried out by known methods, such as radical polymerization using radical-generating agents such as azoisobutyronitrile and peroxide, and ionic polymerization using catalysts such as alkyllithium and Grignard reagent.

[0384] As a solvent used for the polymerization reaction, commercially available products that are generally available may be used. As such a solvent, various types of solvents, such as alcohols, ethers, hydrocarbons, and halogenated solvents, may be appropriately used within a range that does not inhibit the reaction. As a range that does not inhibit the reaction, the solvent may be used alone or a mixture of multiple solvents. Examples of solvents include the solvents described in this specification.

[0385] The (co)polymer obtained by the polymerization reaction can be purified by known methods. Specifically, this can be done by combining ultrafiltration, crystallization, microfiltration, acid washing, washing with water having an electrical conductivity of 10 mS / m or less, and extraction. By such purification methods, a (co)polymer of desired high purity can be obtained.

[0386] Furthermore, for the purpose of removing metal impurities such as metal ions and metal oxides contained in the obtained (co)polymer, a purification method for removing metal impurities may be added. For details of the purification method, the method described in the above and examples in this specification may be referenced. The (co)polymer obtained has a content of various metals (e.g., Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti) contained in the (co)polymer that is typically 10 ppb or less, preferably 5 ppb or less, and more preferably 1 ppb or less.

[0387] [Composition comprising an iodine-containing (meth)acrylate compound and / or an iodine-containing (meth)acrylate (co)polymer]

[0388] The composition of the present embodiment (also simply referred to as the “composition”) comprises the iodine-containing (meth)acrylate compound of the present embodiment and / or the iodine-containing (meth)acrylate (co)polymer of the present embodiment. The composition is suitable for lithography technology. The composition can be used for forming a film for lithography, for example, for forming a resist film (i.e., “resist composition”). The composition can be used for forming an upper layer film (i.e., “composition for forming an upper layer film”), forming an intermediate layer (i.e., “composition for forming an intermediate layer film”), and forming a lower layer film (i.e., “composition for forming a lower layer film”), etc. According to the composition of the present embodiment, it is possible to form a film having high sensitivity and also to impart a good resist pattern shape with high resolution.

[0389] The composition can also be used as a composition for forming optical components using lithography technology. Optical components are used in the form of films and sheets. Examples of such optical components include plastic lenses (prism lenses, lenticular lenses, micro lenses, flannel lenses, viewing angle control lenses, and contrast enhancement lenses, etc.), phase difference films, electromagnetic shielding films, prisms, optical fibers, solder resists for flexible printed circuits, plating resists, interlayer insulating films for multilayer printed circuit boards, photosensitive optical waveguides, liquid crystal displays, organic electroluminescence (EL) displays, optoelectronic semiconductor (LED) devices, solid-state imaging devices, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs). The composition can be suitably used as a buried film and planarization film on a photodiode, a planarization film before and after a color filter, a microlens, and a planarization film and conformal film on a microlens, which are components of a solid-state imaging element where a high refractive index is particularly required.

[0390] The composition may include other components, such as a substrate, a solvent, an acid-generating agent, an acid diffusion control agent, and a base-generating agent, as needed. These components may be used individually or in combination of two or more, as needed. Each component is described below.

[0391] <Information>

[0392] The composition may include a substrate.

[0393] In the present embodiment, "substrate" refers to a compound (including resin) other than the iodine-containing (meth)acrylate compound of the present embodiment and the iodine-containing (meth)acrylate (co)polymer of the present embodiment, which is applied as a resist for g-lines, i-lines, KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), extreme ultraviolet (EUV) lithography (13.5 nm), and electron beams (EB) (e.g., substrates for lithography and substrates for resists). These are not particularly limited as long as they are substrates and can be used as substrates in the present embodiment. Examples of substrates include phenol novolak resin, cresol novolak resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, cycloolefin-maleic anhydride copolymer, cycloolefin, vinyl ether-maleic anhydride copolymer; inorganic resist materials having metal elements such as titanium, tin, hafnium, and zirconium; and derivatives thereof. Among these, phenol novolak resin, cresol novolak resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer; inorganic resist materials having metal elements such as titanium, tin, hafnium, and zirconium; and derivatives thereof are preferred in that a finer resist pattern is obtained. These substrates are used either alone or in combination of two or more types.

[0394] Examples of derivatives include those to which dissociable groups and crosslinkable groups have been introduced. Derivatives to which dissociable groups and crosslinkable groups have been introduced can exhibit dissociation and crosslinking reactions through the action of light, acid, etc.

[0395] "Dissociable group" refers to a characteristic group that generates functional groups, such as alkali-soluble groups, which change solubility by cleaving. Examples of alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, sulfonic acid groups, and hexafluoroisopropanol groups, and phenolic hydroxyl groups and carboxyl groups are preferred, and phenolic hydroxyl groups are more preferred.

[0396] "Crosslinkable group" refers to a group that crosslinks in the presence or absence of a catalyst. Examples of crosslinkable groups include, for instance, an alkoxy group having 1 to 20 carbon atoms, a group having an allyl group, a group having a (meth)acryloyl group, a group having an epoxy (meth)acryloyl group, a group having a hydroxyl group, a group having a urethane (meth)acryloyl group, a group having a glycidyl group, and a group having a vinylphenylmethyl group.

[0397] <Solvent>

[0398] The composition may include a solvent.

[0399] A known solvent may be appropriately used as long as it dissolves at least the iodine-containing (meth)acrylate compound of the present embodiment and / or the iodine-containing (meth)acrylate (co)polymer (B) of the present embodiment.Specific examples of solvents include, for example, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, and propylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; and lactic acid esters such as methyl lactic acid, ethyl lactic acid, n-propyl lactic acid, n-butyl lactic acid, and n-amyl lactic acid. Aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, and ethyl propionate; other esters such as methyl methoxypropionate, ethyl methoxypropionate, 3-methyl ethoxypropionate, 3-ethyl ethoxypropionate, 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-3-methylpropionate, 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; Examples include ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), anisole, and cyclohexanone (CHN); amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactones such as γ-lactone; and furans such as tetrahydrofuran.The solvent used in the present embodiment is preferably a safety solvent, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, n-butyl acetate, and ethyl lactic acid, and even more preferably at least one selected from PGMEA, PGME, CHN, CPN, and ethyl lactic acid. These solvents are used either alone or in combination of two or more.

[0400] In the present embodiment, the amount of solid component and the amount of solvent are not particularly limited, but with respect to the total amount of solid component and solvent (100 mass%), it is preferable that the solid component is 1 to 80 mass% and the solvent is 20 to 99 mass%, more preferably the solid component is 1 to 50 mass% and the solvent is 50 to 99 mass%, even more preferably the solid component is 2 to 40 mass% and the solvent is 60 to 98 mass%, and even more preferably the solid component is 2 to 10 mass% and the solvent is 90 to 98 mass%.

[0401] Acid-generating agent

[0402] The composition may include an acid-generating agent.

[0403] In the composition, it is preferable to include one or more acid-generating agents that generate acid directly or indirectly upon irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. For example, the acid-generating agent described in International Publication No. 2013 / 024778 may be used. The acid-generating agent may be used alone or in combination of two or more.

[0404] The amount of acid-generating agent used is preferably 0.001 to 49 mass% with respect to the total mass of the solid component (100 mass%), more preferably 1 to 40 mass%, even more preferably 3 to 30 mass%, and even more preferably 10 to 25 mass%. By using the acid-generating agent within the above range, a pattern profile with high sensitivity and low edge roughness tends to be obtained. In the present embodiment, when acid is generated within the system, the method of generating the acid is not particularly limited. If an excimer laser is used instead of ultraviolet rays such as g-rays and i-rays, finer processing is possible, and further finer processing is possible if electron beams, extreme ultraviolet rays, X-rays, and ion beams are used as high-energy rays.

[0405] Examples of acid-generating agents include compounds disclosed in International Publication No. 2017 / 033943. As for acid-generating agents, acid-generating agents having an aromatic ring are preferred, acid-generating agents having a sulfonate ion having an aryl group are more preferred, and diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluoromethanesulfonate are even more preferred. By using an acid-generating agent, line edge roughness can be reduced.

[0406] Base generating agent

[0407] The composition may include a base-generating agent.

[0408] Explain the case where the base generator is a photobase generator.

[0409] In this embodiment, the photobase generating agent refers to a substance that generates a base upon exposure to light and does not exhibit activity under normal conditions of room temperature and pressure, but generates a base (basic substance) when irradiated with electromagnetic waves and heated as an external stimulus.

[0410] The photobase generating agent may be a known one, and examples include carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamamide derivatives, and oxime derivatives.

[0411] Basic substances generated from photobase generators are not particularly limited, but compounds having amino groups can be cited. Examples of such compounds include polyamines such as monoamines and diamines, and amidines.

[0412] The basic substance generated is preferably a compound having an amino group with higher basicity (higher pKa value of the conjugate acid) in terms of sensitivity and resolution.

[0413] Examples of photobase generators include, for instance, base generators having a cinnamamide structure as disclosed in Japanese Patent Publication No. 2009-80452 and International Publication No. 2009 / 123122; base generators having a carbamate structure as disclosed in Japanese Patent Publication No. 2006-189591 and Japanese Patent Publication No. 2008-247747; base generators having an oxime structure as disclosed in Japanese Patent Publication No. 2007-249013 and Japanese Patent Publication No. 2008-003581; base generators having a carbamoyl oxime structure; and compounds described in Japanese Patent Publication No. 2010-243773. In addition, structures of known base generators may be used.

[0414] Photobase generators may be used as a single type or in combination of two or more types.

[0415] The preferred content of the photobase generating agent in the photosensitive or radiation-reducing resin composition is the same as the preferred content of the photosensitive or radiation-reducing resin composition of the above photogenerator.

[0416] Acid Diffusion Control Agent

[0417] The composition may include an acid diffusion inhibitor.

[0418] In this embodiment, an acid diffusion control agent may be incorporated into the composition to control the diffusion of acid generated from an acid generator by radiation within the resist film, thereby preventing undesirable chemical reactions in unexposed regions. By using an acid diffusion control agent, the storage stability of the composition can be improved. Furthermore, by using an acid diffusion control agent, the resolution of the film formed using the composition of this embodiment can be improved, and since changes in the linewidth of the resist pattern due to variations in the installation time before radiation and the installation time after radiation can be suppressed, the process stability tends to be excellent. Examples of acid diffusion control agents include nitrogen atom-containing basic compounds such as tributylamine, basic sulfonium compounds, and radiodegradable basic compounds such as basic iodine compounds.

[0419] As an acid diffusion control agent, for example, that described in International Publication No. 2013 / 024778 may be used. The acid diffusion control agent may be used as a single type or in combination of two or more types.

[0420] The amount of acid diffusion control agent is preferably 0.001 to 49 mass% with respect to the total mass of the solid component (100 mass%), more preferably 0.01 to 10 mass%, even more preferably 0.01 to 5 mass%, and even more preferably 0.01 to 3 mass%. If the amount of acid diffusion control agent is within the above range, there is a tendency to prevent deterioration of resolution, pattern shape, and dimensional integrity. Furthermore, even if the time from electron beam irradiation to heating after radiation irradiation is prolonged, the deterioration of the shape of the upper layer of the pattern can be suppressed. In addition, if the amount is 10 mass% or less, there is a tendency to prevent deterioration of sensitivity, developability of unexposed areas, etc. By using an acid diffusion control agent, the storage stability and resolution of the composition are improved, and changes in the linewidth of the resist pattern due to variations in the installation time before and after radiation irradiation can be suppressed, so there is a tendency for excellent process stability.

[0421] Other ingredients

[0422] In the composition of the present embodiment, as other components, one or more types of various additives such as crosslinking agents, solubility promoters, solubility control agents, sensitizers, surfactants, and organic carboxylic acids or phosphoric oxo acids or derivatives thereof may be added as necessary.

[0423] (Crosslinking agent)

[0424] The composition may include one or more crosslinking agents. A crosslinking agent refers to a compound capable of crosslinking at least one of the substrate, an iodine-containing (meth)acrylate compound, and an iodine-containing (meth)acrylate (co)polymer. Preferably, the crosslinking agent is an acid crosslinking agent capable of crosslinking the substrate intramolecularly or intermolecularly in the presence of an acid generated from an acid-generating agent. Examples of such acid crosslinking agents include compounds having one or more groups (hereinafter referred to as "crosslinkable groups") capable of crosslinking the substrate.

[0425] As crosslinking groups, for example, (i) hydroxyalkyl groups such as hydroxy (alkyl group having 1 to 6 carbon atoms), alkoxy (alkyl group having 1 to 6 carbon atoms), and acetoxy (alkyl group having 1 to 6 carbon atoms), or groups derived therefrom; (ii) carbonyl groups such as formyl groups and carboxy (alkyl group having 1 to 6 carbon atoms), or groups derived therefrom; (iii) nitrogen-containing groups such as dimethylaminomethyl groups, diethylaminomethyl groups, dimethylolaminomethyl groups, diethylolaminomethyl groups, and morpholinomethyl groups; (iv) glycidyl-containing groups such as glycidyl ether groups, glycidyl ester groups, and glycidyl amino groups; (v) groups derived from aromatic groups such as benzyloxymethyl groups, benzoyloxymethyl groups, allyloxy groups having 1 to 6 carbon atoms (alkyl groups having 1 to 6 carbon atoms), and aralkyloxy groups having 1 to 6 carbon atoms (alkyl groups having 1 to 6 carbon atoms); (vi) polymerizable multiple bond-containing groups such as vinyl groups and isopropenyl groups, etc. As for the crosslinking groups of the crosslinking agent, hydroxyalkyl groups and alkoxyalkyl groups are preferred, and alkoxymethyl groups are more preferred.

[0426] As a crosslinking agent having a crosslinking group, for example, an acid crosslinking agent described in International Publication No. 2013 / 024778 may be used. The crosslinking agent may be used alone or in combination of two or more types.

[0427] The amount of crosslinking agent is preferably 50 mass% or less with respect to the total mass of solid components (100 mass%), more preferably 40 mass% or less, even more preferably 30 mass% or less, and even more preferably 20 mass% or less.

[0428] (Solution accelerator)

[0429] A solubility accelerator is a component that increases the solubility of a solid component in a developer solution when its solubility is too low, thereby appropriately increasing the dissolution rate of the compound during development. It is preferable that the solubility accelerator be of low molecular weight, and examples include low molecular weight phenolic compounds. Examples of low molecular weight phenolic compounds include bisphenols and tris(hydroxyphenyl)methane. These solubility accelerators are used either alone or in combination of two or more types.

[0430] The amount of the solubility accelerator is appropriately adjusted according to the type of solid component used, and with respect to the total mass (100 mass%) of the solid component, 0 to 49 mass% is preferred, 0 to 5 mass% is more preferred, 0 to 1 mass% is even more preferred, and 0 mass% is even more preferred.

[0431] (Solubility control agent)

[0432] A dissolution control agent is a component that controls the solubility of solid components in the developer when their solubility is too high, thereby appropriately reducing the dissolution rate during development. It is desirable that such a dissolution control agent does not undergo chemical changes during processes such as the firing, irradiation, and development of the resist film.

[0433] Examples of solubilizing agents include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. These solubilizing agents are used individually or in combination of two or more.

[0434] The amount of the solvent control agent is appropriately adjusted according to the type of compound used, and with respect to the total mass of the solid component (100 mass%), 0 to 49 mass% is preferred, 0 to 5 mass% is more preferred, 0 to 1 mass% is even more preferred, and 0 mass% is even more preferred.

[0435] (Increase / Decrease System)

[0436] Sensitizers are components that absorb the energy of irradiated radiation, transfer that energy to acid generators, and thereby increase the amount of acid produced, thereby improving the sensitivity of the resist's appearance. Examples of such sensitizers include benzophenones, nonacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers are used either individually or in combination of two or more types.

[0437] The amount of sensitizer is appropriately adjusted according to the type of compound used, and with respect to the total mass of solid components (100 mass%), 0 to 49 mass% is preferred, 0 to 5 mass% is more preferred, 0 to 1 mass% is even more preferred, and 0 mass% is even more preferred.

[0438] (Surfactant)

[0439] A surfactant is a component that has the function of improving the coating properties or striation of a composition, or the developability of a resist. The surfactant may be any of anionic surfactants, cationic surfactants, nonionic surfactants, or amphoteric surfactants. Preferred surfactants include nonionic surfactants. Nonionic surfactants have good affinity with the solvent used in the preparation of the composition, which can further enhance the effect of the composition. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, and polyethylene glycol higher fatty acid diesters. These surfactants may be commercially available products, and examples include, by the following product names: F-Top (registered trademark) (manufactured by Gemco), Mega Pak (registered trademark) (manufactured by Dai Nippon Ink & Chemical Co., Ltd.), Fluorad (manufactured by Sumitomo 3M), Asahi Guard (registered trademark), Suplon (registered trademark) (both manufactured by Asahi Glass Co., Ltd.), Pepol (registered trademark) (manufactured by Toho Chemical Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), and Polyflow (manufactured by Kyoei Chemical Co., Ltd.). These surfactants are used either individually or in combination of two or more types.

[0440] The amount of surfactant incorporated is appropriately adjusted according to the type of solid component used, and is preferably 0 to 49 mass% with respect to the total mass (100 mass%) of the solid component, more preferably 0 to 5 mass%, even more preferably 0 to 1 mass%, and even more preferably 0 mass%.

[0441] (Organic carboxylic acid or phosphoric oxoic acid or its derivative)

[0442] For the purpose of preventing sensitivity degradation or improving the resist pattern shape and mounting stability, the composition may contain an organic carboxylic acid, a phosphoric oxo acid, or a derivative thereof as an optional component. The organic carboxylic acid, the phosphoric oxo acid, or its derivative may be used in combination with an acid diffusion control agent or used alone. Suitable organic carboxylic acids include, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid. Suitable phosphoric oxo acids or their derivatives include phosphoric acids such as phosphoric acid, di-n-butyl phosphate ester, and diphenyl phosphate ester, or derivatives such as their esters; phosphonic acids such as phosphonic acid, dimethyl phosphate ester, di-n-butyl phosphate ester, phenylphosphonic acid, diphenyl phosphate ester, and dibenzyl phosphate ester, or derivatives such as their esters; Examples include phosphinic acid, phenylphosphinic acid, and derivatives such as their esters. Among these, phosphonic acid is more preferred.

[0443] Organic carboxylic acids or phosphoric oxo acids or their derivatives are used either alone or in combination of two or more types. The amount of organic carboxylic acids or phosphoric oxo acids or their derivatives is appropriately adjusted according to the type of compound used, and is preferably 0 to 49 mass% with respect to the total mass of solid components (100 mass%), more preferably 0 to 5 mass%, even more preferably 0 to 1 mass%, and even more preferably 0 mass%.

[0444] Other Additives

[0445] In the composition of the present embodiment, one or more additives other than the above components may be incorporated as needed. Examples of such additives include dyes, pigments, and adhesion promoters. For example, incorporating a dye or pigment is desirable because it can visualize the latent image of the exposed portion and mitigate the effects of halation during exposure. Additionally, incorporating an adhesion promoter is desirable because it can improve adhesion to the substrate. Furthermore, other additives include anti-halation agents, preservative stabilizers, defoaming agents, and shape modifiers. Specifically, examples include 4-hydroxy-4'-methylchalcone. These additives are used either alone or in combination of two or more.

[0446] In the composition of the present embodiment, the total amount of additives (optional components) can be 0 to 99 mass% with respect to the total mass of the solid components (100 mass%), 0 to 49 mass% is preferred, 0 to 10 mass% is more preferred, 0 to 5 mass% is even more preferred, 0 to 1 mass% is even more preferred, and 0 mass% is particularly preferred.

[0447] [Resist Pattern Formation Method]

[0448] The resist pattern forming method of the present embodiment comprises, in this order, a process of forming a film using the composition of the present embodiment, a process of exposing the formed film to light, and a process of forming a pattern by removing the exposed portion of the exposed film using a developer.

[0449] To form a resist pattern from the composition of the present embodiment, a resist film is formed by applying the composition solution onto a substrate, such as a silicon wafer, metal, plastic, glass, and ceramic, by means of a suitable coating means such as a spin coater, a dip coater, and a roller coater. In some cases, a heat treatment is performed in advance at a temperature of about 50°C to 200°C for a predetermined time (typically 15 to 600 seconds), and then exposed through a predetermined mask pattern. The thickness of the film after exposure is, for example, about 0.01 to 20 μm, preferably about 0.05 to 10 μm, more preferably about 0.07 to 2 μm. For exposure, light rays of various wavelengths, such as ultraviolet rays, far ultraviolet rays, electron beams, extreme ultraviolet rays, and X-rays, may be used. As a light source, for example, far ultraviolet rays such as an F2 excimer laser (wavelength 157 nm), an ArF excimer laser (wavelength 193 nm), and a KrF excimer laser (wavelength 248 nm); extreme ultraviolet rays (wavelength 13 nm); X-rays; electron beams, etc. are appropriately selected and used. In addition, exposure conditions such as exposure amount are appropriately selected according to the compound, (co)polymer, and the composition of the composition containing them, and the type of each additive.

[0450] In this embodiment, in order to stably form a high-precision fine pattern, it is preferable to perform a heat treatment at a temperature of 50 to 200°C for at least 30 seconds after exposure. In this case, if the temperature is below 50°C, there is a risk that the difference in sensitivity depending on the type of substrate will widen. Afterwards, a predetermined resist pattern is formed by developing with an alkaline developer under conditions of typically 10 to 50°C for 10 to 200 seconds, preferably 20 to 25°C for 15 to 90 seconds.

[0451] As an alkaline developer, an alkaline aqueous solution is used in which alkaline compounds such as alkali metal hydroxides, ammonia water, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diazabicyclo-[4.3.0]-5-nonene are dissolved to a concentration of typically 1 to 10 weight%, preferably 1 to 3 weight%. These alkaline developers are used either alone or in combination of two or more types. Additionally, a water-soluble organic solvent or a surfactant may be appropriately added to the developer composed of an alkaline aqueous solution.

[0452] In this embodiment, in order to stably form a high-precision fine pattern, a resist pattern may be formed by performing a development treatment with a developer solution mainly composed of an organic solvent after exposure and PEB.

[0453] Various organic solvents are widely used as organic solvents for developing solutions. Examples of such solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. These organic solvents are used either individually or in combination of two or more types.

[0454] It is preferable that the developer contains a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, and an ether-based solvent.

[0455] As ester-based solvents, for example, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, propyl acetate, isopropyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (isopentyl acetate, 3-methylbutyl acetate), 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, isohexyl acetate, heptyl acetate, octyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA; alias 1-methoxy-2-acetoxypropane), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, Diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-Methyl-3-Methoxypentyl Acetate, 3-Methyl-4-Methoxypentyl Acetate, 4-Methyl-4-Methoxypentyl Acetate, Propylene Glycol Diacetate, Methyl Formate, Ethyl Formate, Butyl Formate, Propylate Formate, Ethyl Lactate, Butyl Lactate, Propylate Lactate, Ethyl Carbonate, Propylate Carbonate, Butyl Carbonate, Methyl Pyruvate, Ethyl Pyruvate, Propylate Pyruvate, Butyl Pyruvate, Methyl Acetoacetate, Ethyl Acetoacetate, Methyl Hydroxyisobutyrate, Methyl Propionate, Ethyl Propionate, Propylate, Isopropyl Propionate, Butyl Propionate, Isobutyl Propionate, Pentyl Propionate, Hexyl Propionate, Heptyl Propionate, Butyl Butyl Butyl Propionate,Examples include isobutyl butyrate, pentyl butyrate, hexyl butyrate, isobutyl butyrate, propyl pentamate, isopropyl pentamate, butyl pentamate, pentyl pentamate, ethyl hexanoate, propyl hexanoate, butyl hexanoate, isobutyl hexanoate, methyl heptanoate, ethyl heptanoate, propyl heptanoate, cyclohexyl acetate, cycloheptyl acetate, 2-ethylhexyl acetate, cyclopentyl propionate, 2-methyl hydroxypropionate, 2-ethyl hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate. Among these, butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, methyl hydroxyisobutyrate, and butyl butanoate are preferred, and butyl acetate, isoamyl acetate, and methyl hydroxyisobutyrate are more preferred.

[0456] Examples of ketone-based solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate, and γ-butyrolactone. Among these, 2-heptanone is preferred.

[0457] Alcohol-based solvents include, for example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, 3-methyl-3-pentanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, Alcohols (monohydric alcohols) such as 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, 5-methyl-2-hexanol, 4-methyl-2-hexanol, 4,5-diethyl-2-hexanol, 6-methyl-2-heptanol, 7-methyl-2-octanol, 8-methyl-2-nonal, 9-methyl-2-decanol, and 3-methoxy-1-butanol; glycol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; Examples include glycol ether-based solvents containing hydroxyl groups, such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene glycol monophenyl ether; and the like. Among these, it is preferable to use a glycol ether-based solvent.

[0458] Examples of ether-based solvents include, in addition to the glycol ether-based solvents containing hydroxyl groups mentioned above, glycol ether-based solvents not containing hydroxyl groups such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; aromatic ether solvents such as anisole and phenetol; and dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane, and isopropyl ether. Among these, glycol ether-based solvents not containing hydroxyl groups and aromatic ether solvents such as anisole are preferred.

[0459] Examples of amide solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphorictriamide, and 1,3-dimethyl-2-imidazolidinone.

[0460] Examples of hydrocarbon solvents include, for instance, aliphatic hydrocarbon solvents such as pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, and perfluoroheptane; aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, and dipropylbenzene.

[0461] In addition, unsaturated hydrocarbon solvents may also be used as hydrocarbon solvents. Examples of such solvents include unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, and hexadecene. The number of double or triple bonds in the unsaturated hydrocarbon solvent is not particularly limited and may also be located at any position in the hydrocarbon chain. Furthermore, when the unsaturated hydrocarbon solvent has double bonds, cis and trans bodies may be mixed.

[0462] Meanwhile, in the case of an aliphatic hydrocarbon solvent, which is a hydrocarbon solvent, it may be a mixture of compounds with the same number of carbon atoms and different structures. For example, when decane is used as an aliphatic hydrocarbon solvent, compounds with the same number of carbon atoms and different structures, such as 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isooctane, may be included in the aliphatic hydrocarbon solvent.

[0463] In addition, the compounds having the same number of carbon atoms and different structures may include only one type, or may include multiple types as described above.

[0464] In addition to the developer composed of the above organic solvent, a known basic compound, a known water-soluble organic solvent, and a known surfactant may be appropriately added.

[0465] [Method for preparing a (co)polymer having a hydroxyl group represented by formula (Y)]

[0466] In the practical application thereof, the (co)polymer of the present embodiment may be made into a (co)polymer having a hydroxyl group represented by formula (Y) as a hydroxyl group by hydrolyzing some or all of the acyl groups. Such a (co)polymer is obtained by including a process of hydrolyzing the acyl groups in the iodine-containing (meth)acrylate (co)polymer of the present embodiment. Since the stability of the compound is high, the (co)polymer containing the compound as a constituent unit is also highly stable, and by using such a (co)polymer, a (co)polymer having a hydroxyl group useful for resist materials can be efficiently and stably manufactured.

[0467] [Chemical Formula 36]

[0468]

[0469] In equation (Y), R 1 , R 2 , A', n 1 , and n 2The above is as described above, and the symbol * indicates a connection point with an adjacent constituent unit.

[0470] Hydrolysis can be carried out by known methods, such as hydrolysis by acid and hydrolysis by base.

[0471] Suitable acid catalysts include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromide, and hydrofluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; and solid acids such as silicotic acid, phosphotungtic acid, silicotic molybdic acid, and phosphomolybdic acid.

[0472] Suitable basic catalysts include, for example, amine-containing catalysts such as pyridine and ethylenediamine, and non-amine basic catalysts such as metal salts. Potassium salts and acetates are preferred as metal salts. Examples of such catalysts include potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide, and magnesium oxide.

[0473] Non-amine base catalysts are commercially available, for example, from EM Science and Aldrich.

[0474] These catalysts are used either alone or in combination of two or more types.

[0475] The amount of catalyst used can be appropriately set according to the substrate, catalyst, and reaction conditions used, and is not particularly limited, but generally, 1 to 5,000 parts by mass per 100 parts by mass of reaction raw material is suitable, and from the perspective of yield, 50 to 3,000 parts by mass is preferable.

[0476] This reaction may be carried out in an organic solvent. As organic solvents, a wide variety of organic solvents are used, including polar aprotic organic solvents and protonic polar organic solvents. A single protonic polar solvent and a single polar aprotic solvent may be used. Furthermore, a mixture of polar aprotic solvents, a mixture of protonic polar solvents, a mixture of polar aprotic solvents and protonic polar solvents, and a mixture of aprotic or protonic solvents and non-polar solvents may be used, and a polar aprotic solvent or a mixture thereof is preferred. The solvent is effective but not an essential component. Suitable polar aprotic solvents include, for example, alcohol-based solvents such as methanol and ethanol; ether-based solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme; ester-based solvents such as ethyl acetate and γ-butyrolactone; and nitrile-based solvents such as acetonitrile. Examples include hydrocarbon solvents such as toluene and hexane; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphorate triamide; and dimethyl sulfoxide. Among these, tetrahydrofuran and dimethyl sulfoxide are preferred. Suitable proton-polar solvents include, for example, di(propylene glycol)methyl ether, di(ethylene glycol)methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol.

[0477] The amount of solvent used can be appropriately set according to the substrate, catalyst, and reaction conditions used, and is not particularly limited, but generally, 0 to 10,000 parts by mass per 100 parts by mass of reaction raw material is suitable, and from the perspective of yield, 100 to 2,000 parts by mass is preferable.

[0478] The reaction is carried out by adding an iodine-containing (meth)acrylate (co)polymer, a catalyst, and, if necessary, an organic solvent to a reactor to form a reaction mixture. Any suitable reactor is used for the reaction. The reaction can be carried out by appropriately selecting known methods such as batch, semi-batch, and continuous methods.

[0479] The reaction temperature varies depending on the concentration of the substrate, the stability of the formed product, the selection of the catalyst, and the desired yield, and is not particularly limited. Generally, a temperature of 0 to 200°C is suitable, and from the perspective of yield, a temperature of 0 to 100°C is preferred.

[0480] The reaction pressure varies depending on the substrate concentration, the stability of the formed product, the selection of the catalyst, and the desired yield, and is not particularly limited. The pressure can be controlled by using an inert gas such as nitrogen, and also by using an intake pump, etc. For reactions at high pressure, a conventional pressure reactor including a shaking vessel, a rocker vessel, and a stirred autoclave is used.

[0481] The reaction time varies depending on the concentration of the substrate, the stability of the product formed, the selection of the catalyst, and the desired yield, and is not particularly limited. Typically, most reactions are carried out for less than 12 hours, and a reaction time of 15 to 600 minutes is common.

[0482] Isolation and purification can be carried out after the reaction is completed using a suitable method known in the prior art. For example, the reaction mixture is poured over ice water and extracted in an organic solvent such as ethyl acetate, butyl acetate, and diethyl ether. Subsequently, the product is recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and activated carbon, and methods in combination thereof. Furthermore, a purification method aimed at removing metal impurities may be added to the obtained high-purity monomer to remove metal-containing impurities such as metal ions and metal oxides. For details of the purification method, the methods described in the above and examples in this specification may be referenced. The high-purity monomer obtained has a content of various metals (e.g., Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti) included in the compound that is typically 10 ppb or less, preferably 5 ppb or less, and more preferably 1 ppb or less.

[0483] Examples

[0484] The present embodiment is described in more detail below through examples and comparative examples, but the present embodiment is not limited in any way by these examples.

[0485] [Measurement Method]

[0486] (1) Structure of the compound

[0487] The structure of the compound was determined using a Bruker Advance 600 II spectrometer under the following conditions: 1 H-NMR measurements were performed and verified.

[0488] Frequency: 400MHz

[0489] Solvent: CDCl3, or d6-DMSO

[0490] Internal Standard: TMS

[0491] Measured temperature: 23℃

[0492] (2) Measurement of the content of various metals (impurities) contained in the precipitate

[0493] Using ICP-MS, the content of various metals (Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti) contained in the precipitate was measured under the following measurement conditions.

[0494] Device: Triple Quadrupole ICP-MS (Inductively Coupled Plasma Mass Spectrometer) (Agilent Technologies, Inc. No. 8900 ICP-QQQ (Trademark)

[0495] (Synthesization Example 1-1) Synthesis of MAC-2H35I and Ac-MAC-2H35I

[0496] 90 g (0.24 mol) of 3,5-diiodosalicylaldehyde was dissolved in 900 ml of methanol, and 22.8 g (0.60 mol) of NaBH4 was added at 10°C or below. The mixture was stirred for 3 hours under ice cooling, followed by stirring at 25°C for 16 hours to allow the reaction to proceed, and the methanol was extracted under reduced pressure to concentrate the mixture. Water and ethyl acetate were added to the concentrate to extract the organic phase. Magnesium sulfate was added to this organic phase to dry it, and the solvent was extracted under reduced pressure to obtain a crude product of 2-hydroxy-3,5-diiodobenzyl alcohol. The obtained crude product of 2-hydroxy-3,5-diiodobenzyl alcohol was purified by column chromatography, yielding 82.5 g (yield 91%) of 2-hydroxy-3,5-diiodobenzyl alcohol as described below.

[0497] [Chemical Formula 37]

[0498]

[0499] 10 g (27 mmol) of the 2-hydroxy-3,5-diiodobenzyl alcohol obtained above was dissolved in 100 mL of dichloromethane, 3.1 g (39 mmol) of pyridine was added under ice cooling, and 4.1 g (27 mmol) of methacrylic anhydride was added dropwise. The reaction was continued by stirring for 4 hours under ice cooling and 18 hours at room temperature. After the reaction was finished, water was added to the reaction solution and washed with an aqueous sodium bicarbonate solution. Magnesium sulfate was added to the organic phase to dry it, and after concentration, it was purified by column chromatography to obtain 9 g (yield 88%) of the target product MAC-2H35I shown below.

[0500] As a result of performing NMR measurements on the obtained compound (MAC-2H35I) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (MAC-2H35I).

[0501] δ(ppm)(CDCl3): 7.2~8.0(2H, Ph), 7.6(1H, -OH), 6.2(1H, =CH2), 5.7(1H, =CH2), 5.1(2H, -CH2-), 2.0(3H, -CH3)

[0502] [Chemical Formula 38]

[0503]

[0504] 9 g (20 mmol) of MAC-2H35I obtained above was dissolved in 100 mL of dimethyl sulfoxide, and 2 eq. of acetic anhydride and 1 eq. of sulfuric acid were added. The temperature was then raised to 80°C and the mixture was stirred and reacted for 3 hours. After the reaction was finished, water was added to the reaction solution and washed with an aqueous sodium bicarbonate solution. Magnesium sulfate was added to the organic phase and dried. After concentration, the mixture was purified by column chromatography to obtain 6 g of the target product Ac-MAC-2H35I (yield 60%) as described below.

[0505] As a result of performing NMR measurements on the obtained compound (Ac-MAC-2H35I) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (Ac-MAC-2H35I).

[0506] δ(ppm)(CDCl3): 7.2~8.0(2H, Ph), 6.2(1H, =CH2), 5.7(1H, =CH2), 5.1(2H, -CH2-), 2.2(3H, -CH3), 2.0(3H, -CH3)

[0507] [Chemical Formula 39]

[0508]

[0509] (Synthesization Example 2-1) Synthesis of MAC-4H35I and Ac-MAC-4H35I

[0510] 128 g (0.78 mol) of calcium chloride and 191.3 g (2.4 mol) of NaBH4 were dissolved in 2.8 L of ethanol, and 410 g (1.1 mol) of 4-hydroxy-3,5-diiodobenzaldehyde was added to this under ice cooling. After reacting by stirring at 25°C for 18 hours, 10 L of water was added, and the pH was adjusted to 2.5 with hydrochloric acid. The precipitate was filtered, washed with water, and dried to obtain 401 g (yield 97%) of 4-hydroxy-3,5-diiodobenzyl alcohol as shown below.

[0511] [Chemical Formula 40]

[0512]

[0513] 400 g (1.06 mol) of the 4-hydroxy-3,5-diiodobenzyl alcohol obtained above was dissolved in 2.8 L of toluene, 916 g (10.6 mol) of methacrylic anhydride, 20 g (0.105 mol) of p-toluenesulfonic acid monohydrate, and 13 mg (0.01 mmol) of 4-methoxyphenol were added, and the mixture was stirred for 2 hours under reflux at 110°C. After the reaction, 4 L of water was added to dry the organic layer, and the mixture was purified by recrystallization twice with hexane to obtain 158 g (yield 33%) of the target product MAC-4H35I shown below.

[0514] As a result of performing NMR measurements on the obtained compound (MAC-4H35I) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (MAC-4H35I).

[0515] δ(ppm)(CDCl3): 9.7(1H, -OH), 7.8(2H, Ph), 6.7(1H, =CH2), 5.0(1H, =CH2), 5.0(2H, -CH2-), 1.9(3H, -CH3)

[0516] [Chemical Formula 41]

[0517]

[0518] 50.0 g of the obtained compound (MAC-4H35I) was dissolved in 100 mL of toluene. Subsequently, the solution was subjected to two separate treatments using 100 mL of 0.1 N aqueous sulfuric acid solution, followed by one separate treatment using 100 mL of 0.1 mmol / L aqueous oxalic acid solution. Afterward, the solution was washed multiple times with 100 mL of ultrapure water until the pH of the aqueous layer recovered after the separate treatment reached 4 or higher. The obtained toluene solution was concentrated to obtain a toluene solution with a solid content of 50%. 1 L of hexane was added to the solution to obtain 41.1 g of precipitate (MAC-4H35Ip).

[0519] As a result of performing NMR measurements on the obtained precipitate under the above measurement conditions, it was confirmed that the precipitate is identical to the compound (MAC-4H35I).

[0520] In addition, regarding the obtained precipitate, the metal (impurity) content was measured under the above measurement conditions, and it was confirmed that for any of the metals Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti, it was 1 ppb or less.

[0521] 9 g (20 mmol) of MAC-4H35I obtained above was dissolved in 100 mL of dimethyl sulfoxide, and 2 eq. of acetic anhydride and 1 eq. of sulfuric acid were added. The temperature was then raised to 80°C and the reaction was carried out by stirring for 3 hours. After the reaction was finished, water was added to the reaction solution and washed with an aqueous sodium bicarbonate solution. Magnesium sulfate was added to the organic phase and dried. After concentration, the mixture was purified by column chromatography to obtain 6 g (yield 60%) of the target product Ac-MAC-4H35I shown below.

[0522] As a result of performing NMR measurements on the obtained compound (Ac-MAC-4H35I) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (Ac-MAC-4H35I).

[0523] 7.8(2H, Ph), 6.7(1H, =CH2), 5.0(1H, =CH2), 5.0(2H, -CH2-), 2.0(3H, -CH3), 1.9(3H, -CH3)

[0524] [Chemical Formula 42]

[0525]

[0526] 50.0 g of the obtained compound (Ac-MAC-4H35I) was dissolved in 100 mL of toluene. Subsequently, the solution was subjected to two separate treatments using 100 mL of 0.1 N aqueous sulfuric acid solution, followed by one separate treatment using 100 mL of 0.1 mmol / L aqueous oxalic acid solution. Afterward, the solution was washed multiple times with 100 mL of ultrapure water until the pH of the aqueous layer recovered after the separate treatment reached 4 or higher. The obtained toluene solution was concentrated to obtain a toluene solution with a solid content of 50%. 1 L of hexane was added to the solution to obtain 38.4 g of precipitate (Ac-MAC-4H35Ip).

[0527] As a result of performing NMR measurements on the obtained precipitate under the above measurement conditions, it was confirmed that the precipitate is identical to the compound (Ac-MAC-4H35I).

[0528] In addition, regarding the obtained precipitate, the metal (impurity) content was measured under the above measurement conditions, and it was confirmed that for any of the metals Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti, it was 1 ppb or less.

[0529] (Synthesization Example 3-1) Synthesis of ACLAC-2H35I and Ac-ACLAC-2H35I

[0530] In a 300 mL branch flask equipped with a Dean Stark and a reflux tube, 10.2 g (27 mmol) of 2-hydroxy-3,5-diiodobenzyl alcohol obtained in Synthesis Example 1-1 was dissolved in 100 mL of toluene, 0.05 g (0.3 mmol) of p-toluenesulfonic acid was added under ice cooling, and 2.9 g (27 mmol) of acrylate chloride was added dropwise. The reaction was continued for 1 hour under reflux conditions with stirring. After the reaction was finished, water was added to the reaction solution, washed with an aqueous sodium bicarbonate solution, magnesium sulfate was added to the organic phase to dry it, and after concentration, purified by column chromatography to obtain 9.3 g (yield 73%) of the target product ACLAC-2H35I as described below.

[0531] As a result of performing NMR measurements on the obtained compound (ACLAC-2H35I) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (ACLAC-2H35I).

[0532] δ(ppm)(CDCl3): 7.2~8.0(2H, Ph), 9.6(1H, -OH), 6.0(1H, =CH2), 6.6(1H, =CH2), 5.1(2H, -CH2-)

[0533] [Chemical Formula 43]

[0534]

[0535] 9.3 g (20 mmol) of the ACLAC-2H35I obtained above was dissolved in 100 mL of dimethyl sulfoxide, and 2 eq. of acetic anhydride and 1 eq. of sulfuric acid were added. The temperature was then raised to 80°C and the reaction was carried out by stirring for 3 hours. After the reaction was finished, water was added to the reaction solution, washed with an aqueous sodium bicarbonate solution, magnesium sulfate was added to the organic phase to dry it, and after concentration, purified by column chromatography to obtain 5.1 g (yield 50%) of the target product Ac-ACLAC-2H35I shown below.

[0536] As a result of performing NMR measurements on the obtained compound (Ac-ACLAC-2H35I) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (Ac-ACLAC-2H35I).

[0537] δ(ppm)(CDCl3): 7.2~8.0(2H, Ph), 6.0(1H, =CH2), 6.6(1H, =CH2), 5.1(2H, -CH2-), 2.0(3H, -CH3)

[0538] [Chemical Formula 44]

[0539]

[0540] (Synthesization Example 4-1) Synthesis of MAC-ADIOH and Ac-MAC-ADIOH

[0541] 2.3 g (12.5 mmol) of 1,3,5-adamantantriol (Mitsubishi Gas Chemical) was dissolved in 100 mL of toluene, 28.1 g (125 mmol) of 57% aqueous hydrogen iodide solution was added, and the reaction was carried out by stirring at 80°C for 13 hours. After the reaction, water was added, washed with sodium bicarbonate, and the organic layer was concentrated and then separated and purified by column chromatography, thereby obtaining 0.9 g of 3-iod-1,5-dihydroxyadamantan represented by the following formula.

[0542] [Chemical Formula 45]

[0543]

[0544] 4.04 g (10 mmol) of 5-iod-1,3-dihydroxyadamantan was dissolved in chloroform, 0.96 g (12 mmol) of pyridine was added under ice cooling, and 1.25 g (12 mmol) of chloride methacrylate was added dropwise. The reaction was continued by stirring for 1 hour under ice cooling and 3 hours at room temperature. After the reaction was finished, water was added to the reaction solution, washed with an aqueous solution of saturated sodium bicarbonate, sodium sulfate was added to the organic phase to dry it, and after concentration, purified by column chromatography to obtain 3.5 g of the target product MAC-ADIOH as described below.

[0545] As a result of performing NMR measurements on the obtained compound (MAC-ADIOH) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (MAC-ADIOH).

[0546] δ(ppm)(d-DMSO): 6.4~6.5(2H, =CH2), 1.5~3.9(14H, Ad-H, -C(CH3)=C), 4.5(1H, -OH)

[0547] [Chemical Formula 46]

[0548]

[0549] 50.0 g of the obtained compound (MAC-ADIOH) was dissolved in 100 mL of methyl ethyl ketone. Subsequently, the solution was subjected to two separate treatments using 100 mL of 0.1 N aqueous sulfuric acid solution, followed by one separate treatment using 100 mL of 0.1 mmol / L aqueous oxalic acid solution. Afterward, the solution was washed multiple times with 100 mL of ultrapure water until the pH of the aqueous layer recovered after the separate treatment reached 4 or higher. The obtained methyl ethyl ketone solution was concentrated to obtain a methyl ethyl ketone solution with a solid content of 50%. 1 L of hexane was added to the solution to obtain 41.1 g of precipitate (MAC-ADIOHp).

[0550] As a result of performing NMR measurements on the obtained precipitate under the above measurement conditions, it was confirmed that the precipitate is identical to the compound (MAC-ADIOH).

[0551] In addition, regarding the obtained precipitate, the metal (impurity) content was measured under the above measurement conditions, and it was confirmed that for any of the metals Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti, it was 1 ppb or less.

[0552] 3.5 g (10 mmol) of the MAC-ADIOH obtained above was dissolved in 100 mL of dimethyl sulfoxide, and 2 eq. of acetic anhydride and 1 eq. of sulfuric acid were added. The temperature was then raised to 80°C and the reaction was carried out by stirring for 3 hours. After the reaction was finished, water was added to the reaction solution, washed with an aqueous sodium bicarbonate solution, magnesium sulfate was added to the organic phase to dry it, and after concentration, purified by column chromatography to obtain 2.4 g (yield 60%) of the target product Ac-MAC-ADIOH shown below.

[0553] As a result of performing NMR measurements on the obtained compound (Ac-MAC-ADIOH) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (Ac-MAC-ADIOH).

[0554] δ(ppm)(CDCl3): 6.4~6.5(2H, =CH2), 1.5~3.9(14H, Ad-H, -C(CH3)=C), 2.0(3H, -CH3)

[0555] [Chemical Formula 47]

[0556]

[0557] 50.0 g of the obtained compound (Ac-MAC-ADIOH) was dissolved in 100 mL of methyl ethyl ketone. Subsequently, the solution was subjected to two separate treatments using 100 mL of 0.1 N aqueous sulfuric acid solution, followed by one separate treatment using 100 mL of 0.1 mmol / L aqueous oxalic acid solution. Afterward, the solution was washed multiple times with 100 mL of ultrapure water until the pH of the aqueous layer recovered after the separate treatment reached 4 or higher. The obtained methyl ethyl ketone solution was concentrated to obtain a methyl ethyl ketone solution with a solid content of 50%. 1 L of hexane was added to the solution to obtain 41.1 g of precipitate (Ac-MAC-ADIOHp).

[0558] As a result of performing NMR measurements on the obtained precipitate under the above measurement conditions, it was confirmed that the precipitate is identical to the compound (Ac-MAC-ADIOH).

[0559] In addition, regarding the obtained precipitate, the metal (impurity) content was measured under the above measurement conditions, and it was confirmed that for any of the metals Na, K, Ca, Mg, Fe, Cu, Ni, Sn, Ag, Mo, Mn, Zn, Co, Al, Pb, Cr, and Ti, it was 1 ppb or less.

[0560] (Synthesization Example 5-1) Synthesis of MAC-ADI4H4M

[0561] 2.3 g (12.5 mmol) of 4-methyl-adamantan-1,4-diol was dissolved in 100 mL of toluene, 11.2 g (50 mmol) of 57% aqueous hydrogen iodide solution was added, and the reaction was carried out by stirring at 80°C for 8 hours. After the reaction, water was added, washed with sodium bicarbonate, and after concentrating the organic layer, separation and purification were performed by column chromatography to obtain 1.1 g of 1-iodo-4-methyl-4-hydroxyadamantan represented by the following formula.

[0562] [Chemical Formula 48]

[0563]

[0564] 2.92 g (10 mmol) of 1-iod-4-methyl-4-hydroxyadamantan was dissolved in chloroform, 0.96 g (12 mmol) of pyridine was added under ice cooling, and 1.25 g (12 mmol) of chloride methacrylate was added dropwise. The reaction was continued by stirring for 1 hour under ice cooling and 3 hours at room temperature. After the reaction was finished, water was added to the reaction solution, washed with an aqueous solution of saturated sodium bicarbonate, sodium sulfate was added to the organic phase to dry it, and after concentration, purified by column chromatography to obtain 3.1 g of the target product MAC-ADI4H4M as described below.

[0565] As a result of performing NMR measurements on the obtained compound (MAC-ADI4H4M) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (MAC-ADI4H4M).

[0566] δ(ppm)(d-DMSO): 6.4~6.5(2H, =CH2), 1.2~2.4(19H, Ad-H, Ad-CH3, -C(CH3)=C)

[0567] [Chemical Formula 49]

[0568]

[0569] (Synthesization Example 1) Synthesis of P-Ac-MAC-2H35I Resin

[0570] 2.4 g of Ac-MAC-2H35I obtained in Synthesis Example 1-1, 3.0 g of 2-methyl-2-adamantyl methacrylate, 2.0 g of γ-butyrolactone methacrylic acid ester, and 1.5 g of 3-hydroxy-1-adamantyl methacrylic acid ester were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated resin was filtered and dried under reduced pressure to obtain a white powdery resin represented by the following chemical formula (P-Ac-MAC-2H35I). The molecular weight (Mw) of this resin was 15400, and the degree of dispersion (Mw / Mn) was 2.2. In addition, 13As a result of measuring C-NMR, the compositional ratio (molar ratio) of the following chemical formula (P-Ac-MAC-ADIOH) was a:b:c:d = 40:30:15:15. Meanwhile, the following chemical formula (P-Ac-MAC-2H35I) is described briefly to indicate the ratio of each constituent unit, but P-Ac-MAC-2H35I is not a block copolymer in which each constituent unit forms an independent block.

[0571] [Chemical Formula 50]

[0572]

[0573] (Synthesization Example 2) Synthesis of P-Ac-MAC-4H35I Resin

[0574] A resin represented by the following chemical formula (P-Ac-MAC-4H35I) was obtained by the same method as in Synthesis Example 1, except that Ac-MAC-4H35I (2.4g) obtained in Synthesis Example 2-1 was used instead of Ac-MAC-2H35I (2.4g) of Synthesis Example 1. The molecular weight (Mw) of this resin was 15,000, and the degree of dispersion (Mw / Mn) was 2.1. In addition, 13 As a result of measuring C-NMR, the compositional ratio (molar ratio) of the following chemical formula (P-Ac-MAC-4H35I) was a:b:c:d = 40:30:15:15. Meanwhile, the following chemical formula (P-Ac-MAC-4H35I) is described briefly to indicate the ratio of each constituent unit; P-Ac-MAC-4H35I is not a block copolymer in which each constituent unit forms an independent block.

[0575] [Chemical Formula 51]

[0576]

[0577] (Synthesization Example 3) Synthesis of P-Ac-MAC-ADIOH1 Resin

[0578] A resin represented by the following chemical formula (P-Ac-MAC-ADIOH1) was obtained by the same method as in Synthesis Example 1, except that Ac-MAC-ADIOH (2.0 g) obtained in Synthesis Example 4-1 was used instead of Ac-MAC-2H35I (2.4 g) of Synthesis Example 1. The molecular weight (Mw) of this resin was 15800, and the degree of dispersion (Mw / Mn) was 1.8. In addition, 13 As a result of measuring C-NMR, the compositional ratio (molar ratio) of the following chemical formula (P-Ac-MAC-ADIOH1) was a:b:c:d = 40:30:15:15. Meanwhile, the following chemical formula (P-Ac-MAC-ADIOH1) is described briefly to indicate the ratio of each constituent unit; P-Ac-MAC-ADIOH1 is not a block copolymer in which each constituent unit forms an independent block.

[0579] [Chemical Formula 52]

[0580]

[0581] (Synthesization Example 4) Synthesis of P-Ac-MAC-ADIOH2 Resin

[0582] A resin represented by the following chemical formula (P-Ac-MAC-ADIOH2) was obtained by the same method as in Synthesis Example 1, except that as monomers (raw materials), 4.7 g of MAC-ADI4H4M obtained in Synthesis Example 5-1, 2.0 g of γ-butyrolactone methacrylic acid ester, and 4.0 g of Ac-MAC-ADIOH obtained in Synthesis Example 4-1 were used. The molecular weight (Mw) of this resin was 15800, and the degree of dispersion (Mw / Mn) was 2.3. In addition, 13 As a result of measuring C-NMR, the compositional ratio (molar ratio) of the following chemical formula (P-Ac-MAC-ADIOH2) was a:b:c = 40:30:30. Meanwhile, the following chemical formula (P-Ac-MAC-ADIOH2) is described briefly to indicate the ratio of each constituent unit; P-Ac-MAC-ADIOH2 is not a block copolymer in which each constituent unit forms an independent block.

[0583] [Chemical Formula 53]

[0584]

[0585] (Synthesization Example 5) Synthesis of P-Ac-MAC-ADIOH3 Resin

[0586] A resin represented by the following chemical formula (P-Ac-MAC-ADIOH3) was obtained by the same method as in Synthesis Example 1, except that as monomers (raw materials), 4.7 g of MAC-ADI4H4M obtained in Synthesis Example 5-1, 2.0 g of γ-butyrolactone methacrylic acid ester, 0.6 g of 4-hydroxystyrene, and 2.0 g of Ac-MAC-ADIOH obtained in Synthesis Example 4-1 were used. The molecular weight (Mw) of this resin was 15,500, and the degree of dispersion (Mw / Mn) was 2.1. In addition, 13 As a result of measuring C-NMR, the compositional ratio (molar ratio) of the following chemical formula (P-Ac-MAC-ADIOH3) was a:b:c:d = 40:30:15:15. Meanwhile, the following chemical formula (P-Ac-MAC-ADIOH3) is described briefly to indicate the ratio of each constituent unit, but P-Ac-MAC-ADIOH3 is not a block copolymer in which each constituent unit forms an independent block.

[0587] [Chemical Formula 54]

[0588]

[0589] (Synthesization Example 6) Synthesis of P-Ac-MAC-ADIOH4 Resin

[0590] A resin represented by the following chemical formula (P-Ac-MAC-ADIOH4) was obtained by the same method as in Synthesis Example 1, except that as monomers (raw materials), 4.7 g of MAC-ADI4H4M obtained in Synthesis Example 5-1, 2.0 g of γ-butyrolactone methacrylic acid ester, 1.9 g of 3,5-diiodo-4-hydroxystyrene, and 2.0 g of Ac-MAC-ADIOH obtained in Synthesis Example 4-1 were used. The molecular weight (Mw) of this resin was 15600, and the degree of dispersion (Mw / Mn) was 2.3. In addition, 13As a result of measuring C-NMR, the compositional ratio (molar ratio) of the following chemical formula (P-Ac-MAC-ADIOH4) was a:b:c:d = 40:30:15:15. Meanwhile, the following chemical formula (P-Ac-MAC-ADIOH4) is described briefly to indicate the ratio of each constituent unit, but P-Ac-MAC-ADIOH4 is not a block copolymer in which each constituent unit forms an independent block.

[0591] [Chemical Formula 55]

[0592]

[0593] (Comparative Synthesis Example 1) Synthesis of P-AC-1 Resin

[0594] A resin represented by the following chemical formula (P-AC-1) was obtained by synthesizing in the same manner as Synthesis Example 1, except that Ac-MAC-2H35I was not used. The molecular weight (Mw) of this resin was 13,500, and the degree of dispersion (Mw / Mn) was 2.3.

[0595] [Chemical Formula 56]

[0596]

[0597] In the above formula (P-AC-1), “40”, “40”, and “20” represent the molar ratios of each constituent unit. Formula (P-AC-1) is described briefly to indicate the ratio of each constituent unit, but P-AC-1 is not a block copolymer in which each constituent unit forms an independent block.

[0598] (Example 1)

[0599] The P-Ac-MAC-2H35I resin solution obtained in Synthesis Example 1 was applied onto a silicon wafer and baked at 110 to 130°C for 60 seconds to form a photoresist layer with a film thickness of 100 nm. Here, the resin solution was prepared by mixing 5 parts by mass of P-Ac-MAC-2H35I resin, 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate, 0.1 parts by mass of tributylamine, and 92 parts by mass of PGMEA (propylene glycol monomethyl ether acetate).

[0600] Next, the photoresist layer was exposed using an electron beam drawing device (ELIONIX ELS-7500 (product name), 50 keV), baked at 115°C for 90 seconds (PEB, post-exposure bake), and developed at 23°C for 60 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) to obtain a positive pattern. From the obtained pattern, the resolution (50 nmL / S) was evaluated using a scanning electron microscope (Hitachi High Technologies S-4800).

[0601] In addition, the obtained resin solution was filled into a light-shielding bottle and stored at 40°C for 30 days. After that, the change in the resin solution over time after storage was evaluated by the following method.

[0602] That is, the resin solution before and after preservation was applied to separate silicon wafers using a spin coater, and heat treatment was performed on a hot plate at 110°C for 1 minute to form a resist layer with a film thickness of 80 nm.

[0603] Next, for each obtained resist layer, 1 mJ / cm² was applied using an extreme ultraviolet (EUV) exposure device “EUVES-7000” (product name, manufactured by Risotec Japan Co., Ltd.) 2 From 1 mJ / cm² 2 80 mJ / cm² 2 Maskless shot exposure was performed with varying exposure doses up to 1 mJ / cm² 2A wafer was obtained having locations where the resist layer was exposed at different exposure doses. Subsequently, the entire surface of the wafer was baked (PEB) at 110°C for 90 seconds and developed using isoamyl acetate at 23°C for 60 seconds. For each of the 80 locations obtained after development, the film thickness was measured using an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), and film thickness profile data for each exposure dose was acquired. The exposure dose at which the slope of the film thickness variation amount relative to the exposure dose is greatest was determined as the sensitivity value (mJ / cm²). 2 It was calculated using ) and used as an indicator of the EUV sensitivity of the resist layer.

[0604] And, using the sensitivity values ​​before and after preservation, the rate of change was calculated by the following indicators.

[0605] "Fluctuation Rate (%)" = [("Sensitivity Value of Resin Solution Before Preservation" - "Sensitivity Value of Resin Solution After Preservation") / "Sensitivity Value of Resin Solution Before Preservation"] × 100

[0606] Using the obtained variation rate, the change over time of the resin solution was evaluated as follows. Meanwhile, a variation rate of less than 2% indicates that the storage stability of the resist composition is good, preventing defects in micro-processing, and also indicates excellent productivity.

[0607] A: Fluctuation rate less than 2%

[0608] B: Fluctuation rate of 2% or more

[0609] The results for resolution, sensitivity, and time are shown in Table 1.

[0610] (Examples 2-6)

[0611] A resin solution was prepared in the same manner as in Example 1, except that the respective resins obtained in Synthesis Examples 2 to 6 were used instead of the P-Ac-MAC-2H35I resin, and a photoresist layer was formed using this resin solution. Next, the resolution and sensitivity were evaluated using each photoresist layer in the same manner as in Example 1. In addition, the change over time was evaluated using each resin solution in the same manner as in Example 1. The respective results are shown in Table 1.

[0612] (Comparative Example 1)

[0613] A resin solution was prepared in the same manner as in Example 1, except that the P-AC-1 resin obtained in Comparative Example 1 was used instead of the P-Ac-MAC-2H35I resin, and a photoresist layer was formed using this resin solution. Next, the resolution and sensitivity were evaluated using the photoresist layer in the same manner as in Example 1. In addition, the change over time was evaluated using the resin solution in the same manner as in Example 1. The results are shown in Table 1.

[0614] [Table 1]

[0615]

[0616] As described above, the iodine-containing (meth)acrylate compound and the iodine-containing (meth)acrylate (co)polymer of the present embodiment can obtain a composition capable of forming a resist film having excellent stability, high sensitivity, and high resolution.

[0617] (Synthesization Example 7) Synthesis of P-MAC-2H35I Resin

[0618] 5.0 g of the P-Ac-MAC-2H35I resin obtained in Synthesis Example 1 was dissolved in 45 mL of tetrahydrofuran, and 0.5 g of 37 mass% hydrochloric acid was added to the solution. After stirring at 50°C for 5 hours, 45 mL of butyl acetate and 45 mL of water were added to the reaction solution to perform liquid-separation purification. Furthermore, the organic layer was concentrated under reduced pressure, redissolved in propylene glycol monomethyl ether, and then added to a large volume of water. The precipitated resin was filtered and dried under reduced pressure to obtain a white powdery resin represented by the following chemical formula (P-MAC-2H35I). The acetyl group converted to a hydroxyl group is, 1 It was confirmed by H-NMR. The molecular weight (Mw) of this resin was 14,400, and the degree of dispersion (Mw / Mn) was 2.2. In addition, 13 As a result of measuring C-NMR, the compositional ratio (molar ratio) of the following chemical formula (P-MAC-2H35I) was a:b:c:d = 40:30:15:15. Meanwhile, the following chemical formula (P-MAC-2H35I) is described briefly to indicate the ratio of each constituent unit; P-MAC-2H35I is not a block copolymer in which each constituent unit forms an independent block.

[0619] [Chemical Formula 57]

[0620]

[0621] (Synthesization Example 8) Synthesis of P-MAC-4H35I Resin

[0622] A P-MAC-4H35I resin represented by the following structural formula was synthesized using the same method as in Synthesis Example 7, except that the P-Ac-MAC-4H35I resin obtained in Synthesis Example 2 was used instead of the P-Ac-MAC-2H35I resin. Meanwhile, the acetyl group converted to a hydroxyl group is, 1 It was confirmed by H-NMR. In addition, 13As a result of measuring C-NMR, the compositional ratio (molar ratio) of the following chemical formula (P-MAC-4H35I) was a:b:c:d = 40:30:15:15. The following chemical formula (P-MAC-4H35I) is described briefly to indicate the ratio of each constituent unit; however, P-MAC-4H35I is not a block copolymer in which each constituent unit forms an independent block.

[0623] [Chemical Formula 58]

[0624]

[0625] (Synthesization Example 9) Synthesis of P-MAC-ADIOH1 Resin

[0626] A P-MAC-ADIOH1 resin represented by the following structural formula was synthesized using the same method as in Synthesis Example 7, except that the P-Ac-MAC-ADIOH1 resin obtained in Synthesis Example 3 was used instead of the P-Ac-MAC-2H35I resin. Meanwhile, the acetyl group converted to a hydroxyl group is, 1 It was confirmed by H-NMR. In addition, 13 As a result of measuring C-NMR, the compositional ratio (molar ratio) of the following chemical formula (P-MAC-ADIOH1) was a:b:c:d = 40:30:15:15. The following chemical formula (P-MAC-ADIOH1) is described briefly to indicate the ratio of each constituent unit; however, P-MAC-ADIOH1 is not a block copolymer in which each constituent unit forms an independent block.

[0627] [Chemical Formula 59]

[0628]

[0629] (Synthesization Example 10) Synthesis of P-MAC-ADIOH2 Resin

[0630] A P-MAC-ADIOH2 resin represented by the following structural formula was synthesized using the same method as in Synthesis Example 7, except that the P-Ac-MAC-ADIOH2 resin obtained in Synthesis Example 4 was used instead of the P-Ac-MAC-2H35I resin. Meanwhile, the acetyl group converted to a hydroxyl group is, 1 It was confirmed by H-NMR. In addition, 13 As a result of measuring C-NMR, the compositional ratio (molar ratio) of the following chemical formula (P-MAC-ADIOH2) was a:b:c = 40:30:30. The following chemical formula (P-MAC-ADIOH2) is described briefly to indicate the ratio of each constituent unit; however, P-MAC-ADIOH2 is not a block copolymer in which each constituent unit forms an independent block.

[0631] [Chemical Formula 60]

[0632]

[0633] (Synthesization Example 11) Synthesis of P-MAC-ADIOH3 Resin

[0634] A P-MAC-ADIOH3 resin represented by the following structural formula was synthesized using the same method as in Synthesis Example 7, except that the P-Ac-MAC-ADIOH3 resin obtained in Synthesis Example 5 was used instead of the P-Ac-MAC-2H35I resin. Meanwhile, the acetyl group converted to a hydroxyl group is, 1 It was confirmed by H-NMR. In addition, 13 As a result of measuring C-NMR, the compositional ratio (molar ratio) of the following chemical formula (P-MAC-ADIOH3) was a:b:c:d = 40:30:15:15. The following chemical formula (P-MAC-ADIOH3) is described briefly to indicate the ratio of each constituent unit; however, P-MAC-ADIOH3 is not a block copolymer in which each constituent unit forms an independent block.

[0635] [Chemical Formula 61]

[0636]

[0637] (Synthesization Example 12) Synthesis of P-MAC-ADIOH4 Resin

[0638] A P-MAC-ADIOH4 resin represented by the following structural formula was synthesized using the same method as in Synthesis Example 7, except that the P-Ac-MAC-ADIOH4 resin obtained in Synthesis Example 6 was used instead of the P-Ac-MAC-2H35I resin. Meanwhile, the acetyl group converted to a hydroxyl group is, 1 It was confirmed by H-NMR. In addition, 13 As a result of measuring C-NMR, the compositional ratio (molar ratio) of the following chemical formula (P-MAC-ADIOH4) was a:b:c:d = 40:30:15:15. The following chemical formula (P-MAC-ADIOH4) is described briefly to indicate the ratio of each constituent unit; however, P-MAC-ADIOH4 is not a block copolymer in which each constituent unit forms an independent block.

[0639] [Chemical Formula 62]

[0640]

[0641] This application is based on Japanese patent application filed on May 15, 2020 (JP 2020-085904), the contents of which are incorporated herein by reference.

[0642] Industrial applicability

[0643] According to the present embodiment, a compound and a method for manufacturing the compound, a (co)polymer and a composition, and a method for forming a resist pattern using the composition can be provided, which is capable of forming a film that is compatible with resist materials, has high stability, high sensitivity, and high resolution. In addition, by using the compound and the (co)polymer, a method can be provided to efficiently manufacture a (co)polymer having hydroxyl groups useful for resist materials.

[0644] The compounds, (co)polymers, and compositions of the present embodiment are widely and effectively utilized, for example, in electrical insulating materials, resins for resists, encapsulating resins for semiconductors, adhesives for printed circuit boards, electrical laminates mounted on electrical equipment, electronic equipment, industrial equipment, etc., matrix resins for prepregs mounted on electrical equipment, electronic equipment, industrial equipment, etc., build-up laminate materials, resins for fiber-reinforced plastics, encapsulating resins for liquid crystal display panels, paints, various coating agents, adhesives, coating agents for semiconductors, resins for semiconductor resists, and resins for forming a resist underlayer.

Claims

Claim 1 Iodine-containing (meth)acrylate compound represented by formula (1). (Equation (1), R 1 Representing silver, a hydrogen atom, a methyl group, or a halogen, R 2 Each represents, independently, a hydrogen atom, a straight-chain organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms, A represents an organic group having 1 to 30 carbon atoms, A represents benzene or adamantane having at least one acetoxy group, and n 1 represents 0 or 1, and n 2 represents an integer from 1 to 20. Claim 2 In claim 1, the above formula (1) is an iodine-containing (meth)acrylate compound in which formula (2). (In Equation (2), R 1 , A, and n 2 is the same as above.). Claim 3 In paragraph 2, the above formula (2) is an iodine-containing (meth)acrylate compound in which formula (3). (In formula (3), B represents an organic group having 5 to 30 carbon atoms including an aromatic group, B represents benzene having at least one acetoxy group, and R 1 , and n 2 is the same as above.). Claim 4 In claim 1, the above formula (1) is an iodine-containing (meth)acrylate compound of formula (3'). (In formula (3'), B' represents an organic group having 5 to 30 carbon atoms including a ring, B' represents an adamantane having at least one acetoxy group, and R 1 , and n 2 is the same as above.). Claim 5 In paragraph 1, n 2 An iodine-containing (meth)acrylate compound in which α represents an integer from 2 to 20. Claim 6 Iodine-containing (meth)acrylate (co)polymer having a constituent unit represented by formula (4). (Equation (4), R 1 Representing silver, a hydrogen atom, a methyl group, or a halogen, R 2 Each represents, independently, a hydrogen atom, a straight-chain organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms, A represents an organic group having 1 to 30 carbon atoms, A represents benzene or adamantane having at least one acetoxy group, and n 1 represents 0 or 1, and n 2 represents an integer from 1 to 20, and the symbol * indicates a connection point with an adjacent constituent unit. Claim 7 In claim 6, the above formula (4) is an iodine-containing (meth)acrylate (co)polymer in which formula (5). (In Equation (5), R 1 , n 2 , A, and the symbol* are the same as above.). Claim 8 In claim 7, the above formula (5) is an iodine-containing (meth)acrylate (co)polymer in which formula (6). (In formula (6), B represents an organic group having 5 to 30 carbon atoms including an aromatic group, B represents benzene having at least one acetoxy group, and R 1 , n 2 , and the symbol* are the same as above.). Claim 9 In claim 6, the above formula (4) is an iodine-containing (meth)acrylate (co)polymer in which formula (6'). (In formula (6'), B' represents an organic group having 5 to 30 carbon atoms including a ring, B' represents an adamantane having at least one acetoxy group, and R 1 , n 2 , and the symbol* are the same as above.). Claim 10 In Paragraph 6, n 2 Iodine-containing (meth)acrylate (co)polymer, where α represents an integer from 2 to 20. Claim 11 A composition comprising the iodine-containing (meth)acrylate compound described in claim 1. Claim 12 A composition according to claim 11, further containing a solvent. Claim 13 A composition according to claim 11 or 12, further containing an acid-generating agent. Claim 14 A composition according to claim 11 or 12, further containing an acid diffusion control agent. Claim 15 A method for forming a resist pattern, comprising: a process of forming a film using a composition described in claim 11; a process of exposing the film formed in the process; and a process of forming a pattern by removing the exposed portion of the film exposed in the process using a developer. Claim 16 A method for producing an iodine-containing (meth)acrylate compound as described in claim 1, comprising a process of reacting an iodine-containing hydroxyl compound represented by formula (a) with a (meth)acrylic acid compound represented by formula (b), and a process of reacting the reactant obtained in the above process with an acylating agent. (wherein in formula (a), A' represents an organic group having 1 to 30 carbon atoms, A' represents a benzene or adamantane having at least one hydroxyl group, and R 2 , n 1 , and n 2 is the same as above.) (in Equation (b), R 1 Eun is identical to the above, and R B Is , It is a hydroxyl group, halogen, (meth)acryloyloxy group, or alkoxy group.) Claim 17 In claim 16, a method for preparing an iodine-containing (meth)acrylate compound in which the above formula (a) is formula (a1). (in Equation (a1), A', and n 2 is the same as above.). Claim 18 A method for preparing an iodine-containing (meth)acrylate compound, wherein, in paragraph 16, the above formula (a) is formula (a2). (In formula (a2), B'' represents an organic group having 5 to 30 carbon atoms including an aromatic group, B'' represents a benzene having at least one hydroxyl group, and n 2 is the same as above.). Claim 19 A method for preparing an iodine-containing (meth)acrylate compound, wherein, in claim 16, the above formula (a) is formula (a3). (in formula (a3), B''' represents an organic group having 5 to 30 carbon atoms containing a cycloaliphatic group, B''' represents an adamantane having at least one hydroxyl group, and n 2 is the same as above) Claim 20 In Paragraph 16, n 2 A method for preparing an iodine-containing (meth)acrylate compound, wherein α represents an integer from 2 to 20. Claim 21 A method for producing a (co)polymer having a hydroxyl group represented by formula (Y), comprising a process of hydrolyzing an acetoxy group in an iodine-containing (meth)acrylate (co)polymer described in claim 6. (Equation(Y), R 1 Representing silver, a hydrogen atom, a methyl group, or a halogen, R 2 Each represents, independently, a hydrogen atom, a straight-chain organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms, A' represents an organic group having 1 to 30 carbon atoms, A' represents benzene or adamantane having at least one hydroxyl group, and n 1 represents 0 or 1, and n 2 represents an integer from 1 to 20, and the symbol * indicates a connection point with an adjacent constituent unit. Claim 22 A composition comprising the iodine-containing (meth)acrylate (co)polymer described in paragraph 6.

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